TWI590001B - Touch panel, radiation-sensitive resin composition and cured film - Google Patents

Description

Touch panel, radiation sensitive resin composition and cured film

The present invention relates to a touch panel, a radiation sensitive resin composition, and a cured film.

In recent years, in the personal digital assistant (PDA), notebook personal computer (Note Personal Computer), office automation equipment (Office Automation Equipment, OA machine) and car navigation system (Car Navigation System) In electronic devices, touch panels are prevalently used as input devices for such displays.

The touch panel can be operated by an electronic device by touching (pressing) the surface thereof with an operator's finger, a pen, or the like, and outputting the data of the touch operation to various processing devices. The touch panel is an input device that becomes a keyboard, and in the above-described electronic device or the like, information input can be easily performed by a dialog form.

In the touch panel, there are a resistive film method, a capacitive method, an infrared method, an ultrasonic method, and an electromagnetic induction coupling method depending on the operation principle.

In such a touch panel, for example, a plurality of first detecting electrodes extending in a predetermined direction, such as a capacitive method, intersecting therewith A touch panel having a structure in which a second detecting electrode extending upward is combined and disposed on a transparent substrate such as glass. The detecting electrodes are respectively guided to the ends of the transparent substrate by electrically connected wiring. At the other end of the wiring connected to the detecting electrode, for example, a terminal for connecting the touch panel is formed.

Further, in the electrostatic capacitance method, for example, as disclosed in Patent Document 1, it is known that the first detecting electrode and the second detecting electrode are disposed on the same layer on one surface of the transparent substrate.

Each of the first detecting electrode and the second detecting electrode of the touch panel described in Patent Document 1 includes a plurality of electrode pads having a rhombic shape and a large area, and connecting a narrower shape than the electrode pads between the electrodes. Connect the part. Further, the first detecting electrode and the second detecting electrode intersect each other at the respective connecting portions, but a translucent interlayer insulating film is disposed at the intersecting portion. Therefore, the touch panel of Patent Document 1 is configured such that the first detecting electrode and the second detecting electrode are overlapped at the respective connecting portions via the interlayer insulating film to ensure insulation. Further, the first detecting electrodes and the second detecting electrodes are respectively guided to the ends of the transparent substrate by wires that are electrically connected. A terminal for connecting the touch panel is formed at the other end of the wiring connected to the detecting electrode.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-310551

[Patent Document 2] International Publication No. 2006/025347

The touch panel having such a configuration includes a detecting electrode on the insulating substrate, and a wiring for electrically connecting the detecting electrode to the detecting electrode to the end portion of the substrate. In the touch panel, the wiring connected to each of the detecting electrodes is not a touch operator directly for detecting an operator's finger or the like. That is, in the touch panel, the formation region of the wiring connected to each of the detecting electrodes is a region that is not used in the touch operation and its detection.

Therefore, it is preferable that the wiring forming area is small and narrow in the touch panel. By narrowing the wiring forming region as described above, the touch panel can greatly set an operation region in which the operator's finger or the like touches and performs a touch operation.

In the touch panel, in order to narrow the wiring formation region, it is preferable to form the wirings electrically connected to the detecting electrodes in a thin manner. Therefore, it is required to form a wiring using a material having a low resistance. In the touch panel, the wiring connected to the detecting electrode can be, for example, a metal wiring using a metal such as copper, and the resistance can be reduced.

However, when a touch panel is a glass substrate or the like as a substrate, for example, the adhesion between the metal wiring including copper and the substrate is low. The touch panel is required to be resistant to deformation when the operator actually touches and presses the operation area with a finger. In short, it is required that the touch panel does not cause defects such as peeling of constituent members such as wiring from the substrate. Further, in order to suppress defects such as disconnection or peeling of the detecting electrode or the wiring, the touch panel can be used for a long period of time, and high reliability is required.

In Patent Document 2, a copper alloy obtained by adding a suitable additive element to copper (Cu) forms an oxide film to form a film, and suppresses Cu oxygen. The interface between the insulating layer adjacent to the film is formed to prevent mutual diffusion. Thereby, copper wiring which is highly conductive and excellent in adhesion to a substrate is provided.

However, there is a problem in that the adhesion between the coating film of such an oxide film and the protective film of the wiring provided to cover the copper wiring as the organic film is low, and moisture from the outside penetrates and corrodes the copper wiring.

The present invention has been made in view of the above problems. In other words, it is an object of the present invention to provide a metal wiring having a metal wiring formed of a metal oxide film and a cured film which is an organic film covering the metal wiring, and having high reliability and high reliability. Touch panel.

Further, an object of the present invention is to provide a radiation-sensitive resin composition for forming a cured film which covers a metal wiring of a touch panel and has good adhesion to the metal wiring.

Further, an object of the present invention is to provide a cured film which covers a metal wiring of a touch panel and has good adhesion to the metal wiring.

According to a first aspect of the present invention, in a touch panel, the touch panel includes a metal wiring and a cured film covering at least a portion of the metal wiring, wherein the metal wiring includes copper or copper. a metal wiring of a second metal element, wherein the cured film is formed using a radiation sensitive resin composition containing (A) a photosensitive agent, and (B) an alkoxyalkyl group At least one of a compound and a hydrolysis condensate of the compound.

In the first aspect of the invention, it is preferable that the metal wiring is formed by including a first layer containing copper, an oxide containing a second metal element other than copper, and covering at least a part of the first layer. The second layer of metal wiring.

In a first aspect of the invention, it is preferred that the second metal element is selected from the group consisting of lithium, lanthanum, cerium, tin, lanthanum, cerium, lanthanum, phosphorus, manganese, magnesium, calcium, nickel, zinc, lanthanum. At least one of the group consisting of aluminum, lanthanum, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium.

In the first aspect of the invention, it is preferable that the second metal element is manganese.

In the first aspect of the invention, it is preferred that the cured film is formed using a radiation-sensitive resin composition further containing (C) an alkali-soluble resin.

In a first aspect of the invention, it is preferable that the component (C) of the radiation-sensitive resin composition for forming the cured film comprises a component selected from the group consisting of an acrylic resin having a carboxyl group, a polyamine, and a polyoxyalkylene. At least one of the groups.

In the first aspect of the invention, it is preferred that the cured film is formed using a radiation sensitive resin composition further containing (D) an antioxidant.

In a first aspect of the invention, it is preferred that the cured film is further used to contain (F) as comprising an element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, indium, tin, antimony, bismuth, antimony, bismuth. And a radiation sensitive linear resin composition of the inorganic oxide particles of the oxide of at least one element of the group formed by the group.

In the first aspect of the invention, it is preferred that the component (A) of the radiation sensitive resin composition forming the cured film contains a photoacid generator and a photopolymerization initiator. At least one of them.

In the first aspect of the invention, it is preferable that the component (B) of the radiation sensitive resin composition forming the cured film contains at least an amine group, a block amine group, an isocyanate group, and a blocked isocyanate group. a compound of one.

A second aspect of the present invention relates to a radiation sensitive resin composition comprising at least one of (A) a photosensitive agent, and (B) a compound containing an alkoxyalkyl group and a hydrolysis condensate of the compound. The radiation sensitive linear resin composition is characterized in that: a cured film for forming a touch panel, the touch panel comprising a metal wiring and the cured film covering at least a portion of the metal wiring, the metal wiring A second layer comprising a first layer containing copper and an oxide containing a second metal element other than copper and covering at least a part of the first layer.

In the second aspect of the invention, it is preferred to further comprise (C) an alkali-soluble resin.

In a second aspect of the present invention, preferably, in the case of containing (C) an alkali-soluble resin, the component (C) comprises an acrylic resin, a polyamine, and a polyoxyalkylene selected from the group consisting of a carboxyl group. At least one of the groups.

In a second aspect of the invention, it is preferable that the oxide of the second metal element contained in the second layer of the metal wiring is selected from the group consisting of lithium, lanthanum, cerium, tin, lanthanum, cerium, An oxide of at least one element of the group consisting of ruthenium, phosphorus, manganese, magnesium, calcium, nickel, zinc, lanthanum, aluminum, lanthanum, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium.

In a second aspect of the invention, it is preferred to further comprise (D) an anti- Oxidizer.

In the second aspect of the invention, it is preferred to further comprise (E) a polyfunctional (meth) acrylate.

In a second aspect of the invention, it is preferred to further comprise (F) as a group comprising a group selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, indium, tin, antimony, bismuth, antimony, bismuth and antimony. A group of inorganic oxide particles of an oxide of at least one element.

In the second aspect of the invention, it is preferred that the component (A) contains at least one of a photoacid generator and a photopolymerization initiator.

In the second aspect of the invention, it is preferred that the component (B) contains at least one compound having an amine group, a block amine group, an isocyanate group, and a blocked isocyanate group.

A third aspect of the present invention relates to a cured film which is a cured film formed of a radiation sensitive resin composition containing (A) a sensitizer and (B) At least one of a compound of an alkoxyalkyl group and a hydrolysis condensate of the compound is characterized in that: At least a part of the metal wiring for covering the touch panel including the metal wiring, the metal wiring including a first layer containing copper and an oxide containing a second metal element other than copper and covering the first layer The second layer formed by at least a part of the method.

According to the first aspect of the present invention, a film having a metal wiring, a metal wiring formed of a metal oxide film, and an organic film covering the metal wiring is obtained. A touch panel having a good adhesion of a cured film and having high reliability.

According to the second aspect of the present invention, a radiation-sensitive resin composition for forming a cured film covering the metal wiring of the touch panel and having good adhesion to the metal wiring is obtained.

According to the third aspect of the present invention, a cured film covering the metal wiring of the touch panel and having good adhesion to the metal wiring is obtained.

21‧‧‧ touch panel

22‧‧‧Transparent substrate

23‧‧‧1st detecting electrode

24‧‧‧2nd detection electrode

25‧‧‧hard film

28‧‧‧Intersection

29‧‧‧Interlayer insulating film

30‧‧‧electrode pads

31‧‧‧Wiring

32‧‧‧Bridge wiring

41‧‧‧1st floor

42‧‧‧2nd floor

1 is a plan view showing an example of a touch panel according to a first embodiment of the present invention.

Fig. 2 is a cross-sectional view taken along line BB' of Fig. 1.

FIG. 3 is a cross-sectional view showing an example of a configuration of a wiring included in the touch panel according to the first embodiment of the present invention.

4 is a plan view showing a wiring, a first detecting electrode, and a second detecting electrode formed on a transparent substrate in order to form a touch panel.

5 is a plan view showing a wiring, a first detecting electrode, a second detecting electrode, an interlayer insulating layer, and a bridge wiring formed on a transparent substrate in order to form a touch panel.

Hereinafter, embodiments of the present invention will be appropriately described using the drawings.

Further, in the present invention, the "radiation" irradiated during exposure includes visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Embodiment 1.

<Touch Panel>

A touch panel according to an embodiment of the present invention is a touch panel including a metal wiring and a cured film covering at least a part of the metal wiring. In other words, the touch panel of the present embodiment includes a detecting electrode for detecting a touch operation of an operator's finger or the like on the substrate. Further, the touch panel of the present embodiment includes a wiring electrically connected to the detecting electrode, and the wiring is a metal wiring formed using a metal material. In the touch panel of the present embodiment, the wiring connected to the detecting electrode includes wiring for guiding the detecting electrode to the end portion of the substrate of the touch panel, and includes a portion for connecting the disconnected detecting electrode portions to each other. Wiring. Further, the touch panel of the present embodiment includes a cured film covering at least a part of the metal wiring.

The touch panel of this embodiment can be used as a capacitive touch panel.

1 is a plan view showing an example of a touch panel according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view taken along line BB' of Fig. 1.

As shown in FIG. 1 , the touch panel 21 of the present embodiment includes a first detecting electrode 23 extending in the X direction and a second extending in the Y direction orthogonal to the X direction on the surface of the transparent substrate 22 . The electrode 24 is detected.

The transparent substrate 22 can be a glass substrate. Further, the transparent substrate 22 may be a resin substrate, and in this case, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene film, a polypropylene film, or a polyether oxime may be used. Membrane, polycarbonate An ester film, a polyacrylic acid film, a polyvinyl chloride film, a polyimide film, a ring-opening polymer film of a cyclic olefin, a film containing the hydride thereof, and the like. The thickness of the transparent substrate 22 can be set to 0.1 mm to 3 mm in the case of a glass substrate. In the case of a resin substrate, it can be set to 10 μm to 3000 μm.

A plurality of the first detecting electrodes 23 and the second detecting electrodes 24 are disposed, respectively. Further, the first detecting electrode 23 and the second detecting electrode 24 are arranged in a matrix shape in the operation region of the touch panel 21. The first detecting electrode 23 detects a coordinate in the Y direction of the touch position of the operator. The second detecting electrode 24 detects a coordinate in the X direction of the touch position of the operator. The first detecting electrode 23 and the second detecting electrode 24 are provided on the same layer on the same surface of the transparent substrate 22. Further, the number of the first detecting electrodes 23 and the second detecting electrodes 24 is not limited to the example of FIG. 1, but is preferably determined according to the size of the operation area and the detection accuracy of the required touch position. That is, the touch panel 21 can be configured by using a larger number or a smaller number of the first detecting electrodes 23 and the second detecting electrodes 24.

As shown in FIG. 1, each of the first detecting electrode 23 and the second detecting electrode 24 includes a plurality of electrode pads 30 having a rhombic shape. The first detecting electrode 23 and the second detecting electrode 24 are arranged such that the electrode pad 30 of the first detecting electrode 23 is spaced apart from the electrode pad 30 of the second detecting electrode 24 adjacent thereto. At this time, the gap between the electrode pads 30 is an extremely small gap to the extent that insulation can be ensured.

Further, the first detecting electrode 23 and the second detecting electrode 24 are arranged so as to intersect each other as small as possible. Further, the electrode pads 30 constituting the first detecting electrode 23 and the second detecting electrode 24 are disposed on the entire operation region of the touch panel 21.

As shown in FIG. 1, the electrode pad 30 may have a rhombic shape, but is not limited to such a shape, and may be, for example, a polygonal shape such as a hexagon.

Preferably, each of the first detecting electrode 23 and the second detecting electrode 24 is a transparent electrode. Here, the "transparent electrode" is an electrode having high transmittance for visible light. As the first detecting electrode 23 and the second detecting electrode 24, an electrode including a transparent conductive material such as an electrode including ITO or an electrode containing indium oxide and zinc oxide can be used. When the first detection electrode 23 and the second detection electrode 24 each include ITO, in order to secure sufficient conductivity, it is preferable that the thickness is 10 nm to 100 nm.

The formation of the first detecting electrode 23 and the second detecting electrode 24 can be performed by a known method, and for example, a film containing a transparent conductive material such as ITO can be formed by sputtering or the like, and light lithography can be used. Patterning by law or the like.

As shown in FIGS. 1 and 2, the first detecting electrode 23 and the second detecting electrode 24 are formed on the same surface of the transparent substrate 22, and are formed in the same layer. Therefore, the first detecting electrode 23 and the second detecting electrode 24 intersect at a plurality of locations in the operation region, and the intersection portion 28 is formed.

In the touch panel 21 of the present embodiment, as shown in FIG. 2, in the intersection portion 28, any one of the first detecting electrode 23 and the second detecting electrode 24 is not in contact with the other. open. In other words, the first detecting electrode 23 is connected to the intersection portion 28, but the second detecting electrode 24 extending in the left-right direction of FIG. 2 is formed to be disconnected. Further, a bridge wire 32 is provided in order to electrically connect the portion where the second detecting electrode 24 is interrupted. Between the bridge wiring 32 and the first detecting electrode 23 An interlayer insulating film 29 of a material.

As shown in FIG. 2, in the intersection portion 28, the interlayer insulating film 29 provided on the first detecting electrode 23 is formed of a material having excellent light transmittance. The polysiloxane, the acrylic resin, the acrylic monomer, and the like can be applied by a printing method, and if necessary, patterned, and then heat-hardened to form the interlayer insulating film 29. In the case of forming using polysiloxane, the interlayer insulating film 29 is an inorganic insulating layer containing cerium oxide (SiO ₂ ). Further, when an acrylic resin and an acrylic monomer are used, the interlayer insulating film 29 is an organic insulating layer containing a resin. When SiO ₂ is used for the interlayer insulating film 29, for example, an SiO ₂ film can be formed only on the first detecting electrode 23 of the intersection portion 28 by a sputtering method using a mask to constitute the interlayer insulating film 29.

A bridge wire 32 is provided on the upper layer of the interlayer insulating film 29. The bridge wiring 32 can realize the function of electrically connecting the second detecting electrodes 24 interrupted at the intersection portion 28 to each other as described above. The bridge wire 32 is preferably formed of a material having excellent light transmittance such as ITO. Further, the bridge wiring 32 can also be formed using a metal material having excellent resistance characteristics, and can be used as a metal wiring. The bridge wiring 32 can be made thinner by a metal wiring having excellent resistance characteristics, and can be made inconspicuous to the operator of the touch panel 21. In the touch panel 21, the second detecting electrode 24 can be electrically connected to the Y direction by providing the bridge wiring 32.

As shown in FIG. 2, the first detecting electrode 23 and the second detecting electrode 24 have a shape in which a plurality of rhombic electrode pads 30 are vertically or horizontally arranged as described above. In the first detecting electrode 23, the connecting portion located at the intersection portion 28 becomes the first detecting electrode The rhombic electrode pad 30 of 23 has a narrower width. Further, the bridge wiring 32 is also formed in a strip shape in a shape narrower than the width of the rhombic electrode pad 30.

Terminals (not shown) are respectively provided at the end portions of the first detecting electrode 23 and the second detecting electrode 24 of the touch panel 21, and the wiring 31 is led out from the terminals.

FIG. 3 is a cross-sectional view schematically showing a configuration of a wiring included in the touch panel according to the first embodiment of the present invention.

In the touch panel 21 according to the first embodiment of the present invention, the wiring 31 is a metal wiring. Further, the wiring 31 is preferably a metal wiring including a second metal element other than copper or copper. Moreover, the second metal element is preferably selected from the group consisting of lithium, lanthanum, cerium, tin, lanthanum, cerium, lanthanum, phosphorus, manganese, magnesium, calcium, nickel, zinc, lanthanum, aluminum, lanthanum, gallium, indium, iron. At least one of the group consisting of titanium, vanadium, cobalt, zirconium and hafnium, more preferably manganese.

More specifically, as shown in FIG. 3, it is preferable that the wiring 31 includes a first layer 41 containing copper, a second metal other than copper, and covering at least a part of the surface of the first layer 41. The second layer 42. Further, it is preferable that the first layer 41 of the wiring 31 contains copper or a copper alloy. Further, the second layer 42 of the wiring 31 is preferably made of an oxide of the second metal element other than copper and is formed to cover at least a part of the first layer 41, and more preferably by inclusion. The oxide of the second metal as a main component covers at least a part of the surface of the first layer 41.

Further, in the touch panel 21 of the present embodiment, it is particularly preferable that the second layer 42 covers all of the surface of the first layer 41. In addition, in FIG. 3, schematically The structure of the wiring 31 is shown, and the cross-sectional structure is not limited to a rectangular shape. For example, the cross-sectional shape of the first layer 41 of the wiring 31 may be a square shape, a trapezoidal shape, a parallelogram shape, or the like, and the second layer 42 may cover the surface of the first layer.

In the wiring 31, as a preferable material constituting the first layer 41, copper or a copper alloy can be cited as described above. Moreover, the copper alloy may be selected from the group consisting of lithium, lanthanum, cerium, tin, lanthanum, cerium, lanthanum, phosphorus, manganese, magnesium, calcium, nickel, zinc, lanthanum, aluminum, lanthanum, gallium, indium, iron, titanium, A copper alloy of at least one element of a group consisting of vanadium, cobalt, zirconium and hafnium. That is, a preferable material of the first layer 41 constituting the wiring 31 may be copper or an alloy of copper and the above second metal element.

Further, as a more preferable copper alloy, a copper alloy containing an element having a diffusion coefficient larger than the self-diffusion coefficient of copper can be cited. Specific examples of the more preferable copper alloy include a copper alloy containing at least one additive element selected from the group consisting of lithium, ruthenium, osmium, tin, ruthenium, osmium, iridium, manganese, zinc, gallium, and indium. . In this case, the amount of the additive element added to the copper alloy is preferably in the range of 0.1 atom% to 25 atom% with respect to copper. By setting the addition amount to the range as described above, it is possible to facilitate the diffusion of the additive element in the copper alloy due to heating.

Further, a particularly preferable copper alloy is a copper alloy containing manganese, that is, a copper-manganese alloy.

Further, it is preferable that the wiring 31 is formed by coating the second layer 42 of the first layer 41 with an oxide of a metal element, that is, a metal oxide. In this case, the metal oxide in the second layer 42 is preferably an oxide containing at least a metal other than copper, and more preferably an oxide containing the second metal element other than copper.

Specifically, the metal oxide contained in the second layer 42 may be selected from the group consisting of lithium, lanthanum, cerium, tin, lanthanum, cerium, lanthanum, phosphorus, manganese, magnesium, calcium, nickel, zinc, lanthanum, aluminum, An oxide of at least one element of the group consisting of ruthenium, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium, and more preferably a metal oxide.

The wiring 31 of the structure shown in FIG. 3 can be formed by forming a wiring pattern using the copper alloy exemplified as the preferable constituent material of the first layer 41, and then performing heat treatment.

In other words, the wiring pattern including the copper alloy is heated in the presence of oxygen such as the atmosphere, whereby an oxide of a metal constituting the copper alloy is formed on the surface layer of the wiring pattern. As a result, the wiring 31 is formed, and the wiring 31 includes a first layer 41 containing copper and an oxide containing a metal element other than copper, and is formed by coating the first layer 41. Layer 42.

In this case, as the copper alloy forming the wiring pattern, it is preferable to use a group selected from the group consisting of lithium, ruthenium, osmium, tin, ruthenium, osmium, iridium, manganese, zinc, gallium, and indium as described above. At least one element (the element having a diffusion coefficient larger than the self-diffusion coefficient of copper) is used as a copper alloy to which an element is added. In this case, by the heat treatment, the additive element having a diffusion coefficient larger than the self-diffusion coefficient of copper rapidly reaches the copper surface, and the oxide film layer of the additive element is preferentially formed on the surface of the copper alloy.

Therefore, the second layer 42 of the wiring 31 of the touch panel 21 contains an element other than copper, that is, a group selected from the group consisting of lithium, germanium, antimony, tin, antimony, bismuth, antimony, manganese, zinc, gallium, and indium. At least one element (the element has a self-expansion than copper) A metal oxide having a larger diffusion coefficient is used as a main component.

For example, in order to form the wiring 31, when a copper-manganese alloy containing manganese described above is used, a wiring pattern containing a copper-manganese alloy is formed on a substrate constituting the touch panel. Thereafter, the wiring 31 is formed by heat treatment, and the wiring 31 includes a first layer 41 containing copper or a copper-manganese alloy, and a metal oxide and covering at least a part of the first layer 41. The second layer 42 is constructed. In this case, the metal oxide contained in the first layer 41 may contain an oxide of manganese.

In the touch panel 21, a method of forming the copper alloy for forming the wiring 31 is not particularly limited. For example, the method described in Japanese Laid-Open Patent Publication No. 2008-261895 can be referred to. In other words, a copper alloy can be formed by a physical vapor deposition method such as a plating method such as an electric field plating method or a dissolving plating method, a vacuum vapor deposition method, or a sputtering method. Further, the oxide film layer is formed by heat-treating the copper alloy formed as described above. Therefore, by using a known patterning method together with the above-described method of forming a copper alloy, a wiring pattern including the above-described copper alloy can be obtained, and by heating the wiring 31, the wiring 31 can be formed.

Further, the heat treatment temperature of the copper alloy for forming the wiring 31 is preferably in the range of, for example, 150 ° C to 450 ° C, and the heat treatment time is preferably in the range of, for example, 2 minutes to 5 hours. When the heat treatment temperature is less than 150 ° C, it takes time to form the oxide film, and productivity is lowered. On the other hand, when it exceeds 450 ° C, there is a concern that the other constituent members constituting the touch panel may be adversely affected by deterioration or the like. Further, when the heat treatment time is less than 2 minutes, the film thickness of the metal oxide is thin, and if it exceeds 5 hours, the oxide film is present. There is a concern that it takes too much time to reduce the productivity of the touch panel.

The wiring 31 formed as described above includes the first layer 41 containing copper, and the second layer 42 including the metal oxide formed by the above heating and covering the first layer 41. The first layer 41 of the wiring 31 contains a metal material containing copper and is excellent in electric resistance characteristics. Further, since the wiring 31 includes the second layer 42 including the metal oxide, it can exhibit excellent adhesion to the transparent substrate 22 constituting the touch panel 21.

In particular, when the wiring 31 includes a copper-manganese alloy, the second layer 42 of the wiring 31 contains an oxide of manganese, and exhibits excellent adhesion to the transparent substrate 22 including the above-described constituent material.

Therefore, the touch panel 21 can narrow the formation area of the wiring 31, and can suppress the defects such as peeling of the wiring 31 from the transparent substrate 22, thereby achieving high reliability.

Further, as described above, the touch panel 21 is provided with the bridge wiring 32 electrically connecting the second detecting electrodes 24 interrupted by the intersection portion 28 to each other. The bridge wire 32 can be formed of a material having excellent light transmittance such as ITO as described above. Further, the bridge wiring 32 may be made of the same metal wiring as the wiring 31. In this case, the bridge wiring 32 can be formed in the same manner as the wiring 31 by using the above-described copper alloy in the same manner as the wiring 31. For example, when the wiring 31 is formed, the bridge wiring 32 can be simultaneously formed.

The wiring 31 uses a connection terminal (not shown) at its end, and a position where a voltage is applied to the first detection electrode 23 and the second detection electrode 24 or a touch operation is detected. An external control circuit (not shown) is electrically connected.

As shown in FIG. 1 and FIG. 2, a transparent cured film 25 is disposed on the surface of the transparent substrate 22 on which the first detecting electrode 23 and the second detecting electrode 24 are disposed so as to cover the wiring 31. Similarly, the cured film 25 is disposed so as to cover the first detecting electrode 23 and the second detecting electrode 24. Therefore, when the bridge wiring 32 is the same metal wiring as the wiring 31, the cured film 25 can also cover the wiring 31 and the bridge wiring 32 which is a metal wiring.

The cured film 25 is formed by patterning the wiring 31 in the wiring forming region of the touch panel 21, and covering the first detecting electrode 23 and the second detecting electrode 24 in the operation region. They are protected. In addition, the insulating film 25 is formed by patterning a connection terminal (not shown) of the end portion of the wiring 31 led out from the first detecting electrode 23 and the second detecting electrode 24 to be exposed.

In the touch panel 21, the cured film 25 functions as a protective film covering the wiring 31 and the first detecting electrode 23 and the second detecting electrode 24. Therefore, it is possible to suppress the peeling of the wiring 31 from the transparent substrate 22 and achieve high reliability. Further, deterioration of the first detecting electrode 23 and the second detecting electrode 24 can be suppressed, and high reliability can be achieved.

The radiation sensitive resin composition of the embodiment of the present invention can be used for the formation of the cured film 25. Further, predetermined patterning can be performed on at least a part of the wiring 31 and on the first detecting electrode 23 and the second detecting electrode 24. The radiation sensitive resin composition of the embodiment of the present invention for forming the cured film 25 will be described later in detail. Radiation-sensitive linear tree of an embodiment of the present invention The grease composition is applied to at least a part of the wiring 31 as a metal wiring, and is cured to be a cured film for covering it and protecting it. In this case, the radiation-sensitive resin composition of the embodiment of the present invention can form the cured film 25 without causing corrosion or the like as a wiring 31 of the metal wiring, and serves as a protective film for the wiring 31.

The touch panel 21 can be provided on the surface of the wiring 31 of the transparent substrate 22 and the surface on which the first detecting electrode 23 and the second detecting electrode 24 are formed, for example, by using an adhesive layer (not shown) including an acrylic transparent adhesive. Cover film (not shown).

In the touch panel 21 having the above configuration, in the operation region in which the first detecting electrode 23 and the second detecting electrode 24 are arranged in a matrix, the capacitance is measured, and the electrostatic capacitance generated when a touch operation of an operator's finger or the like is performed The change can detect the contact position of a finger or the like. Further, the touch panel 21 is connected via the wiring 31 electrically connected to the first detecting electrode 23 and the second detecting electrode 24, and is placed on a display such as a liquid crystal display element or an organic EL element, and can be used as a display of an electronic device. The device is used as appropriate.

As described above, in the touch panel of the embodiment of the present invention, the cured film of the embodiment of the protective wiring or the like is an important component.

Next, the radiation sensitive resin composition which is used in the formation of the cured film of the touch panel according to the first embodiment of the present invention, which is the second embodiment of the present invention, will be described in detail.

Embodiment 2.

<Inductive Radiation Resin Composition>

The cured film of the touch panel according to the first embodiment of the present invention can be disposed as described above by covering the wiring on the substrate on which the detecting electrode and the wiring including the metal are disposed, and covering the detection. electrode. The radiation sensitive resin composition according to the second embodiment of the present invention is a radiation sensitive resin composition suitable for forming a cured film of the touch panel.

In particular, when a cured film covering a metal wiring or the like is formed on an oxide of a metal having high reductivity such as manganese, a part of the cured film is reduced, adhesion to the metal wiring is lowered, and wiring is generated due to the incorporation of external moisture. corrosion. Since the cured film formed of the radiation sensitive resin composition of the second embodiment of the present invention is hardly reduced by manganese or the like, the adhesion to the metal wiring can be maintained at a high level.

The radiation sensitive resin composition of the second embodiment of the present invention contains: (A) a photosensitive agent (sometimes abbreviated as "(A) component"), and (B) a compound containing an alkoxyalkyl group and the compound. At least one of the hydrolysis condensate (sometimes referred to simply as "(B) component" or "(B) compound"). Further, it is preferable to contain (C) an alkali-soluble resin (sometimes abbreviated as "(C) component") in addition to the components (A) and (B).

In addition, the radiation sensitive resin composition of the second embodiment of the present invention may contain any component other than the components (A) to (C) as long as the effects of the present invention are not impaired. For example, the radiation sensitive resin composition of the present embodiment may contain (D) an antioxidant (sometimes abbreviated as "(D) component") and (E) a polyfunctional monomer (sometimes abbreviated as "(E) component"). ), (F) inorganic oxide particles (sometimes simple It is called "(F) component").

Hereinafter, each component contained in the radiation sensitive resin composition of the present embodiment will be described.

[(A) sensitizer]

The (A) sensitizer as the component (A) is a photosensitive material and is a material which generates a reactive active species by exposure. (A) The sensitizer preferably contains at least one of, for example, a photoacid generator and a photopolymerization initiator.

[photoacid generator]

A preferred photoacid generator as the (A) sensitizer is a compound which generates an acid by irradiation with radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam (charged particle beam), X-ray, or the like can be used as described above. The radiation sensitive resin composition of the present embodiment contains a photoacid generator as the component (A), whereby the radiation sensitive resin composition of the present embodiment can exhibit positive radiation characteristics.

The photoacid generator which is preferably a photosensitive agent (A) is a compound which generates an acid (for example, a carboxylic acid, a sulfonic acid, or the like) by irradiation with radiation, and is not particularly limited. The form of the photo-acid-producing material in the radiation-sensitive resin composition of the present embodiment may be in the form of a photoacid generator as a compound to be described later, or may be a (C) alkali-soluble resin or the like as described later. The form of the photoacid generating group incorporated in a part of the resin may be in the form of both of them.

Preferred photoacid generators (also referred to as "(A) photoacid generators) as (A) sensitizers include oxime sulfonate compounds, sulfonium salts, sulfonimide compounds, A halogen-containing compound, a diazomethane compound, an anthracene compound, a sulfonate compound, a carboxylate compound, a quinonediazide compound, or the like.

(肟 sulfonate compound)

The above oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (1).

In the above formula (1), R ²¹ is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of the groups may be substituted with a substituent.

In the above formula (1), the alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may also have a bridged alicyclic group such as an alkoxy group having an octal number of 1 to 10 or an alicyclic group (including a 7,7-dimethyl-2-oxo-norbornyl group). Preferred is a bicycloalkyl group or the like. The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may also be substituted with an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

With respect to the compound containing the oxime sulfonate group represented by the above formula (1), a more preferable compound is an oxime sulfonate compound represented by the following formula (2).

, R ²¹ and (1) R in the above formula is synonymous above described formula (2) ^21. X is an alkyl group, an alkoxy group or a halogen atom. M1 is an integer from 0 to 3. When m1 is 2 or 3, a plurality of Xs may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

In the above formula (2), the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom of X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. Particularly preferred is a compound in which the m1 is 1, X is a methyl group, and the substitution position of X is an ortho position in the above formula (2).

Specific examples of the above-mentioned oxime sulfonate compound include a compound (3-i), a compound (3-ii), and a compound (3) represented by the following formulas (3-i) to (3-v), respectively. -iii), compound (3-iv) and compound (3-v).

These compounds may be used singly or in combination of two or more kinds thereof, or may be used in combination with other photoacid generators as the component (A). The above compound (3-i) [(5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], Compound (3-ii) [(5H-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], compound (3-iii) [( Camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], compound (3-iv) [(5-p-toluenesulfonyloxyimino) 5-H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile] and compound (3-v) 2-(octylsulfonyloxyimino)-2-(4-methoxy Phenyl phenyl) acetonitrile is available as a commercial product.

(鎓 salt)

Examples of the above sulfonium salt include a diphenylphosphonium salt, a triphenylsulfonium salt, a phosphonium salt, a benzothiazolium salt, a tetrahydrothiophene salt, a sulfonimide compound, and the like.

Examples of the above sulfonimide compound include N-(trifluoromethylsulfonyloxy) succinimide, N-(camphorsulfonyloxy) succinimide, and N-(4-methylphenyl sulfonate.醯oxy) succinimide, N-(2-trifluoromethylphenylsulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylphenylsulfonyloxy) O-phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide , N-(camphorsulfonyloxy) diphenylmaleimide, and the like.

As the other photoacid generator, a photoacid generator described in JP-A-2011-215503 can be used.

(A) an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, an anthracene compound, a sulfonate compound, and a carboxylate compound of the photoacid generator described above Self-radiation sensitivity, dissolution From the viewpoint of the nature, an oxime sulfonate compound is preferred, and a compound containing the oxime sulfonate group represented by the above formula (1) is more preferred. Further, the oxime sulfonate compound represented by the above formula (2) is more preferable.

Further, in the compound containing the oxime sulfonate group represented by the above formula (1), it is considered to be commercially available, and it is particularly preferred that (5-propylsulfonyloxyimino-5H -thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5H-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) Acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H- Thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile.

Further, as the (A) photoacid generator, it is also preferred for the onium salt, more preferably a tetrahydrothiophene salt and a benzyl phosphonium salt, and particularly preferably 4,7-di-n-butoxy group- 1-naphthyltetrahydrothiophene trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate.

(A) The photoacid generator is any one of an oxime sulfonate compound, a phosphonium salt, a sulfonium imide compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, and a carboxylate compound. In this case, one type may be used alone or two or more types may be used in combination. The (A) photoacid generator is any one of an oxime sulfonate compound, a phosphonium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, and a carboxylate compound. In the case of the radiation-sensitive resin composition of the present embodiment, the content of the (A) photoacid generator is preferably 0.1 part by mass to 10 parts by mass based on 100 parts by mass of the component (B). The mass part is more preferably 1 part by mass to 5 parts by mass. In the case where the radiation-sensitive resin composition of the present embodiment contains the alkali-soluble resin of the component (C) to be described later in detail, the content of the (A) photoacid generator such as the oxime sulfonate compound is It is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the component (C). When the content of the (A) photoacid generator is in the above range, the radiation sensitivity of the radiation sensitive resin composition of the present embodiment can be optimized, and good patterning property can be exhibited, which is suitable for forming the embodiment. The hardened film.

(醌 叠 azide compound)

The photoacid generator which is preferable as the (A) sensitizer of the radiation sensitive resin composition of the present embodiment may be a quinonediazide compound in addition to the oxime sulfonate compound or the like. The quinonediazide compound can be particularly preferably used as a photoacid generator.

The quinonediazide compound is a quinonediazide compound which generates a carboxylic acid by irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "master nucleus") and 1,2-naphthoquinonediazide sulfonium halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other parent cores.

The 1,2-naphthoquinonediazidesulfonium halide is preferably 1,2-naphthoquinonediazidesulfonium chloride. Examples of the 1,2-naphthoquinonediazidesulfonium chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. More preferred among these are 1,2-naphthoquinonediazide-5-sulfonyl chloride.

In the condensation reaction of the phenolic compound or the alcoholic compound (nuclear core) with the 1,2-naphthoquinonediazidesulfonium halide, it is preferred to use the OH group in the phenolic compound or the alcoholic compound. It is equivalent to 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonium halide. The condensation reaction can be carried out by a known method.

As the quinonediazide compound, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0) can be suitably used. a condensate of 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol).

These quinonediazide compounds may be used singly or in combination of two or more.

Further, it may be used in combination with the above sulfonium sulfonate compound, sulfonium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, hydrazine compound, sulfonate compound, and carboxylate compound.

The content of the quinonediazide compound in the radiation sensitive resin composition of the present embodiment is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass based on 100 parts by mass of the component (B). Parts by mass to 50 parts by mass. In the case where the radiation-sensitive resin composition of the present embodiment contains the alkali-soluble resin of the component (C) to be described later in detail, the content of the quinonediazide compound is 100 parts by mass based on the component (C). In other words, it is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 50 parts by mass. By setting the content of the quinonediazide compound to the above range, the difference in solubility between the irradiated portion of the radiation and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer can be increased, and the patterning performance can be improved. Moreover, it can also The cured film obtained by using the radiation sensitive resin composition has good solvent resistance.

[Photopolymerization initiator]

A photopolymerization initiator (also referred to as "(A) photopolymerization initiator") which is a (A) sensitizer is an active species which induces radiation to produce a polymerization initiation of a polymerizable compound. ingredient. The photopolymerization initiator may, for example, be a photoradical polymerization initiator.

(A) The photopolymerization initiator may, for example, be an O-indenyl hydrazine compound, an acetophenone compound, a biimidazole compound or the like. These compounds may be used singly or in combination of two or more.

As the specific example of the (A) photopolymerization initiator, the O-mercaptopurine compound is preferably 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzamide).肟)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetyl), ethyl ketone 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9.H.-carbazol-3-yl]-1-(O-acetamidine)肟) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzoate Mercapto}-9.H.-carbazol-3-yl]-1-(O-acetamidine).

The acetophenone compound which is a specific example of the above (A) photopolymerization initiator is, for example, an α-amino ketone compound or an α-hydroxy ketone compound.

The (A) photopolymerization initiator can be used as a photopolymerization initiator described in JP-A-2013-164471, JP-A-2012-212114, and JP-A-2010-85929. .

The photopolymerization initiator exemplified as the (A) sensitizer may be used alone or Two or more types are used in combination.

The content of the photopolymerization initiator as exemplified as the (A) sensitizer is preferably from 1 part by mass to 40 parts by mass, more preferably from 5 parts by mass to 30 parts by mass per 100 parts by mass of the component (B). Parts by mass. In the case where the radiation-sensitive resin composition of the present embodiment contains the alkali-soluble resin of the component (C) to be described later in detail, it is preferably 1 mass with respect to 100 parts by mass of the component (C). The amount is ~40 parts by mass, more preferably 5 parts by mass to 30 parts by mass. By setting the content of the (A) photopolymerization initiator to 1 part by mass to 40 parts by mass, the radiation sensitive resin composition of the present embodiment can be formed to have high solvent resistance and high even at a low exposure amount. Hardened film with hardness and high adhesion.

[(B) Alkoxyalkylalkyl group-containing compound and hydrolysis condensate thereof]

The component (B) contained in the radiation sensitive resin composition of the present embodiment is at least one of (B) a compound containing an alkoxyalkyl group and a hydrolysis condensate of the alkoxyalkyl group-containing compound (( B) compound).

The compound (B) of the radiation sensitive resin composition of the present embodiment contains an alkoxyalkyl group in the molecule. The alkoxyalkyl group can improve the adhesion to the metal oxide by hydrolysis and condensation reaction.

Therefore, the component (B) contained in the radiation sensitive resin composition of the present embodiment can improve the adhesion between the cured film formed using the radiation sensitive resin composition and the metal wiring of the touch panel, for example.

By containing the component (B), the radiation sensitive resin composition of the present embodiment can provide a cured film excellent in adhesion. Moreover, in particular, it can be provided for the above The wiring of the touch panel as the metal wiring shows a cured film having excellent adhesion.

The component (B) is preferably a compound containing a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an amine group, an isocyanate group or an oxiranyl group, and an alkoxyalkyl group.

Among the components (B), the alkoxyalkyl group is preferably a trimethoxydecyl group, a dimethoxymethyl fluorenyl group, a methoxy dimethyl fluorenyl group, a triethoxy fluorenyl group, or a diethoxy group. Alkyl fluorenyl group, ethoxydiethyl decyl group, and the like.

Further, among the components (B), examples of the compound having a reactive functional group include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, and vinyl triethoxy decyl decane. , vinyl trimethoxy decane, γ-isocyanatopropyl triethoxy decane, γ-aminopropyl trimethoxy decane, γ-glycidoxypropyl trimethoxy decane, β-(3 , 4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. Further, a block amine group or a blocked isocyanate group which is an amine group or an isocyanate group may be regenerated by removing the protecting group by heating by protecting the amine group or the isocyanate group by a specific protecting group.

Specific examples of the compound having a block amine group or a blocked isocyanate group and an alkoxyalkyl group can be exemplified by 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine. a compound in which an amine group of γ-aminopropyltrimethoxydecane is protected by a trimethylsulfonyl group, and an isocyanate group of γ-isocyanatopropyltriethoxydecane is monoethanolamine, diethanolamine or pyrazole. And a compound which is protected by any of methyl ethyl ketone oxime.

Further, examples of the hydrolysis-condensation compound of the above alkoxyalkylalkyl group-containing compound include 3-methylpropenyloxypropyltrimethoxynonane and relative In the case of 3-methacryloxypropyltrimethoxydecane, 1/4 mol of water and 0.05 wt% of phosphoric acid were placed in a flask and hydrolyzed and condensed at 60 ° C.

Further, the component (B) of the radiation sensitive resin composition of the present embodiment is preferably a compound having at least one of an amine group, a block amine group, an isocyanate group, and a blocked isocyanate group.

The content of the component (B) in the radiation-sensitive resin composition of the present embodiment is preferably 0.1% by mass to 50% by mass based on the total mass of the radiation-sensitive resin composition, and includes (C) which will be described later. In the case of the alkali-soluble resin of the component, it is preferably 1 part by mass to 50 parts by mass, more preferably 10 parts by mass to 30 parts by mass, per 100 parts by mass of the component (C).

By including the component (B) in the range of the radiation sensitive resin composition of the present embodiment, it is possible to improve the adhesion to the metal wiring of the touch panel in the cured film of the present embodiment formed using the same. Sex.

[(C) alkali soluble resin]

The alkali-soluble resin ((C) alkali-soluble resin) of the component (C) which can be contained in the radiation-sensitive resin composition of the present embodiment is a resin which is soluble in an alkaline solvent and is an alkali developable resin. (C) The alkali-soluble resin is not particularly limited as long as it is a resin (polymer) having alkali developability in order to form a cured film of a touch panel.

For example, it is preferred that the (C) alkali-soluble resin contains at least one selected from the group consisting of an acrylic resin having a carboxyl group, a polyamine, and a polyoxyalkylene.

The radiation sensitive resin composition of the present embodiment contains (C) an alkali In the case of the soluble resin, as described above, the component (B) is preferably 1 part by mass to 50 parts by mass, more preferably 10 parts by mass to 30 parts by mass based on 100 parts by mass of the (C) alkali-soluble resin. The range of parts by mass. Further, the content of the component (A) is in the group consisting of an oxime sulfonate compound, a phosphonium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, and a carboxylic acid ester compound. In the case of any of 100 parts by mass of the component (C), it is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 1 part by mass to 5 parts by mass. In addition, when the component (A) is a quinonediazide compound, the content thereof is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass based on 100 parts by mass of the component (C). Parts by mass to 50 parts by mass. In addition, when the component (A) is a photopolymerization initiator, the content thereof is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the component (C). Parts by mass ~ 30 parts by mass.

Hereinafter, each of an acrylic resin, a polyamine, and a polyoxyalkylene having a carboxyl group as a (C) alkali-soluble resin will be described in more detail.

[Acrylic resin with carboxyl group]

The acrylic resin having a carboxyl group as the (C) alkali-soluble resin is preferably a constituent unit having a carboxyl group and a constituent unit having a polymerizable group. In this case, the structural unit having a carboxyl group and the structural unit having a polymerizable group are not particularly limited as long as they have alkali developability (alkali solubility).

The constituent unit having a polymerizable group is preferably at least one constituent unit selected from the group consisting of a constituent unit having an epoxy group and a constituent unit having a (meth)acryloxy group. Acrylic resin having a carboxyl group by including the above specific By forming a unit, a film having excellent surface hardenability and deep hardenability is formed, and a cured film of an embodiment of the present invention can be formed.

The constituent unit having a (meth) propylene fluorenyloxy group can be formed, for example, by a method of reacting an epoxy group in a copolymer with (meth)acrylic acid, and a carboxyl group in the copolymer and having an epoxy group. Method for reacting (meth) acrylate, method for reacting hydroxyl group in copolymer with (meth) acrylate having isocyanate group, and method for reacting acid anhydride site in copolymer with hydroxy (meth) acrylate Wait. Particularly preferred among these are methods for reacting a carboxyl group in a copolymer with a (meth) acrylate having an epoxy group.

The acrylic resin containing a structural unit having a carboxyl group and a constituent unit having an epoxy group as a polymerizable group may (C1) be at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as It is synthesized by copolymerizing "(C1) compound") and (C2) an epoxy group-containing unsaturated compound (hereinafter also referred to as "(C2) compound"). In this case, the acrylic resin having a carboxyl group is composed of a constituent unit formed of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and an unsaturated compound containing an epoxy group. A copolymer of the constituent units formed.

The acrylic resin having a carboxyl group can be produced, for example, by copolymerizing a compound (C1) which provides a structural unit containing a carboxyl group and a compound (C2) which provides a structural unit containing an epoxy group in the presence of a polymerization initiator in a solvent. . Further, (C3) a hydroxyl group-containing unsaturated compound (hereinafter also referred to as "(C3) compound") which provides a structural unit containing a hydroxyl group may be further added to form a copolymer. In addition, In the production of the acrylic resin having a carboxyl group, the compound (C4) may be further added together with the compound (C1), the compound (C2) and the compound (C3) (providing a compound derived from the above (C1), (C2) and (C3) an unsaturated compound of a constituent unit other than the constituent unit of the compound) to form a copolymer. Next, each compound of (C1) to (C3) will be described in detail.

((C1) compound)

Examples of the (C1) compound include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an acid anhydride of an unsaturated dicarboxylic acid, and a mono[(meth)acryloxyalkylalkyl]ester of a polyvalent carboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.

Examples of the acid anhydride of the unsaturated diacid acid include an acid anhydride of the compound exemplified as the above dicarboxylic acid.

Preferred among the (C1) compounds are acrylic acid, methacrylic acid, maleic anhydride, self-copolymerization reactivity, solubility in an aqueous alkaline solution, and ease of availability, and more preferred are acrylic acid, methacrylic acid, maleic anhydride.

These (C1) compounds may be used singly or in combination of two or more.

The ratio of use of the (C1) compound is preferably 5% by mass to 40% based on the total of the (C1) compound and the (C2) compound (optionally any (C3) compound and (C4) compound). %, more preferably 10% by mass to 25% by mass. By using the ratio of the (C1) compound to 5 mass% to 30 The mass% can optimize the solubility of the acrylic resin having a carboxyl group in an alkaline aqueous solution, and can form a film excellent in radiation sensitivity.

((C2) compound)

The (C2) compound is an epoxy group-containing unsaturated compound. Examples of the epoxy group include an oxoheteryl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, and methyl group. 3,4-epoxybutyl acrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,-3,4-epoxycyclohexylmethyl methacrylate, and the like. From the viewpoints of improvement of copolymerization reactivity and solvent resistance of an insulating film, etc., preferred among these are glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid-6,7. -epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate , 3,4-epoxycyclohexyl acrylate, and the like.

Examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-2-methyloxetane. , 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(2-propene oxime Oxyethyl)oxetane, 3-(2-propenyloxyethyl)-2-ethyloxetane, 3-(2-propenyloxyethyl)-3-B Oxycyclobutane, 3-(2-propenyloxyethyl)-2-phenyloxetane Acrylate; 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methyl Propylene methoxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(2-methylpropene oxime Oxyethyl)oxetane, 3-(2-methylpropenyloxyethyl)-2-ethyloxetane, 3-(2-methylpropenyloxyethyl) 3-ethyloxetane, 3-(2-methylpropenyloxyethyl)-2-phenyloxetane, 3-(2-methylpropenyloxyethyl) a methacrylate such as a 2,2-difluorooxetane or the like.

Preferred among the (C2) compounds are glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-(methacryloxymethyl)-3-ethyl Oxetane. These (C2) compounds may be used singly or in combination of two or more.

The ratio of use of the (C2) compound is preferably 5% by mass to 60% based on the total of the (C1) compound and the (C2) compound (optionally any (C3) compound and (C4) compound). %, more preferably 10% by mass to 50% by mass. By using the ratio of the use of the (C2) compound to 5% by mass to 60% by mass, the cured film of the present embodiment having excellent curability and the like can be formed.

((C3) compound)

The (C3) compound may, for example, be a (meth) acrylate having a hydroxyl group, a (meth) acrylate having a phenolic hydroxyl group, or a hydroxystyrene.

Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxy acrylate. Hexyl ester and the like.

The ratio of use of the (C3) compound is preferably from 1% by mass to 30% based on the total of the (C1) compound, the (C2) compound, and the (C3) compound (optionally any (C4) compound). %, more preferably 5 mass% to 25% by mass.

((C4) compound)

The compound (C4) is not particularly limited as long as it is an unsaturated compound other than the above (C1) compound, (C2) compound and (C3) compound. Examples of the (C4) compound include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a chain alkyl acrylate, a cyclic alkyl acrylate, an aryl methacrylate, and an aryl acrylate. An unsaturated dicarboxylic acid diester, a maleimide compound, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton or the like, and other unsaturated compounds.

These (C4) compounds may be used singly or in combination of two or more.

The ratio of use of the (C4) compound is preferably 10% by mass to 80% by mass based on the total of the (C1) compound, the (C2) compound, and the (C4) compound (and any (C3) compound).

[polyamide]

(C) The alkali-soluble resin is a polymer which has a structure represented by the following general formula (M-1) as a main component. A polymer having a structure represented by the formula (M-1) as a main component may have a quinone ring, an oxazole ring, or the like by heating or a suitable catalyst. A polymer of a cyclic structure. Preferred are polyamido acids or polyphthalamides of polyamidiene precursors or polyhydroxyguanamines of polybenzoxazole precursors. Since it has a ring structure, heat resistance and solvent resistance are drastically improved. Here, the "main component" is n structural units in the structure represented by the general formula (M-1) of 50 mol% or more of all the structural units which have a polymer. It is preferably contained in an amount of 70 mol% or more, more preferably 90 mol% or more.

In the above formula (M-1), R ¹ represents a divalent to octavalent organic group having a carbon number of 2 or more, and represents a structural component of an acid. Examples of the divalent acid of R ¹ include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid, and bis(carboxyphenyl)propane, and cyclohexane dicarboxylic acid. An aliphatic dicarboxylic acid such as an acid or adipic acid. Examples of the acid in which R ^{1 is} a trivalent acid include a tricarboxylic acid such as trimellitic acid or trimesic acid. Examples of the tetravalent acid in which R ^{1 is} a tetravalent acid include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfonium tetracarboxylic acid. An aliphatic tetracarboxylic acid such as an alkyltetracarboxylic acid or a cyclopentanetetracarboxylic acid, and two hydrogen atoms of a carboxyl group of these compounds are a diester compound of a methyl group or an ethyl group. Further, an acid having a hydroxyl group such as hydroxyphthalic acid or hydroxytrimethylenecarboxylic acid may also be mentioned. These acid components may be used in combination of two or more kinds, and preferably contain a residue of 1 mol% to 40 mol% of tetracarboxylic acid. Further, from the viewpoint of solubility or sensitivity to an alkaline developer, a residue containing 50 mol% or more of an acid having a hydroxyl group is preferred.

R ¹ preferably has an aromatic ring from the viewpoint of heat resistance, and more preferably a trivalent or tetravalent organic group having a carbon number of 6 to 30.

In the general formula (M-1), R ² represents a divalent to octavalent organic group having two or more carbon atoms, and represents a structural component of the diamine. From the viewpoint of heat resistance, it is preferred that R ² has an aromatic ring. Specific examples of the diamine include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylphosphonium, and bis(trifluoromethyl). Benzidine, bis(aminophenoxyphenyl)propane, bis(aminophenoxyphenyl)anthracene, bis(amino-hydroxy-phenyl)hexafluoropropane, diaminodihydroxypyrimidine, diamine Dihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, hydrogen of these aromatic rings by alkyl or halogen atom Substituted compounds, or aliphatic cyclohexanediamine, methylene dicyclohexylamine, hexamethylenediamine, and the like.

R ³ and R ^{4 in the} formula (M-1) may be the same or different, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of the solubility in the alkaline developing solution and the solution stability of the obtained photosensitive resin composition, it is preferred that 10 mol% to 90 mol% of each of R ³ and R ⁴ is hydrogen. Further, it is more preferred that R ³ and R ⁴ each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the other is a hydrogen atom.

Further, l and m of the formula (M-1) represent the number of carboxyl groups or ester groups, An integer representing 0~2. It is preferably 1 or 2. p and q of the formula (M-1) represent an integer of 0 to 4, and p+q>0. n of the formula (M-1) represents the number of repeating units of the polymer, and is in the range of 10 to 100,000. When n is less than 10, the solubility of the polymer in the alkaline developing solution is too large, and the contrast between the exposed portion and the unexposed portion is not obtained, and a desired pattern cannot be formed. On the other hand, when n is more than 100,000, the solubility of the polymer in the alkaline developing solution is too small, and the exposed portion is not dissolved, and a desired pattern cannot be formed. From the viewpoint of solubility of the polymer in the alkaline developing solution, n is preferably 1,000 or less, more preferably 100 or less. Further, n is preferably 20 or more from the viewpoint of an increase in elongation.

[polyoxyalkylene]

A preferred polyoxyalkylene as the (C) alkali-soluble resin is a polyoxyalkylene having a radically reactive functional group. In the case where the polyoxyalkylene is a polyoxyalkylene having a radically reactive functional group, if the polymer has a radically reactive functional group in a main chain or a side chain of a compound having a siloxane coupling bond, There is no particular limitation. In this case, the polyoxyalkylene can be hardened by radical polymerization, and the hardening shrinkage can be suppressed to a minimum. Examples of the radical reactive functional group include an unsaturated organic group such as a vinyl group, an α-methylvinyl group, an acrylonitrile group, a methacryl fluorenyl group, or a styryl group. From the viewpoint of smoothly performing the hardening reaction, those having an acrylonitrile group or a methacrylonitrile group are preferred.

The polyoxyalkylene as the (C) alkali-soluble resin is preferably a hydrolysis-condensation product of a hydrolyzable decane compound. The hydrolyzable decane compound constituting the polyoxyalkylene preferably contains (s1) a hydrolyzable decane compound represented by the following formula (S-1) (hereinafter Also known as "(s1) compound"), and (s2) a hydrolyzable decane compound of a hydrolyzable decane compound (hereinafter also referred to as "(s2) compound") represented by the following formula (S-2).

In the above formula (S-1), R ¹¹ is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer from 1 to 3. However, when R ¹¹ and R ^{12 are} plural, a plurality of R ¹¹ and R ¹² are independent of each other.

In the above formula (S-2), R ¹³ is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group. n is an integer from 0 to 20. q is an integer from 0 to 3. However, when R ¹³ and R ^{14 are} plural, a plurality of R ¹³ and R ¹⁴ are independent of each other.

In the present invention, the "hydrolyzable decane compound" generally means a compound having a group which is subjected to a temperature range of from room temperature (about 25 ° C) to about 100 ° C in the presence of no catalyst or excess water. Heated, hydrolyzable to form a sterol group or a shape The group of the oxirane condensate. In the hydrolysis reaction of the hydrolyzable decane compound represented by the above formula (S-1) and the above formula (S-2), a part of the hydrolyzable group remains in an unhydrolyzed state in the produced polyoxyalkylene. Here, the "hydrolyzable group" means a group which can be hydrolyzed to form a sterol group or a group which can form a siloxane condensate. Further, in the radiation-sensitive resin composition of the present embodiment, a part of the hydrolyzable decane compound is not hydrolyzed in a part or all of the hydrolyzable group in the molecule, and is not condensed with another hydrolyzable decane compound. The state of the body remains. In addition, the "hydrolysis condensate" is a hydrolysis condensate obtained by condensing a part of sterol groups of the hydrolyzed decane compound. Hereinafter, the (s1) compound and the (s2) compound will be described in detail.

((s1) compound)

In the above formula (S-1), R ¹¹ is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer from 1 to 3. However, when R ¹¹ and R ^{12 are} plural, a plurality of R ¹¹ and R ¹² are independent of each other.

Examples of the alkyl group having 1 to 6 carbon atoms in the above R ¹¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a butyl group. From the viewpoint of easiness of hydrolysis, preferred among these are a methyl group and an ethyl group. From the viewpoint of carrying out the hydrolysis condensation reaction, the above p is preferably 1 or 2, more preferably 1.

The organic group having a radical reactive functional group may be a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms and a carbon number substituted by one or more hydrogen atoms via the radical reactive functional group. It is an aryl group of 6 to 12, an aralkyl group having a carbon number of 7 to 12, and the like. When there are multiple R ^12s in the same molecule, the ones are independent. Further, the organic group represented by R ¹² may have a hetero atom. Examples of such an organic group include an ether group, an ester group, and a thioether group.

Preferred among the (s1) compounds are vinyl trimethoxy decane, p-styryl triethoxy decane, 3-methyl from the viewpoint of achieving high scratch resistance and the like, and the condensation reactivity is high. Propylene methoxy propyl trimethoxy decane, 3-propenyl methoxy propyl trimethoxy decane, 3-methyl propylene oxy propyl triethoxy decane, 3- propylene methoxy propyl three Ethoxy decane, 3-(trimethoxydecyl)propyl succinic anhydride.

((s2) compound)

In the above formula (S-2), R ¹³ is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group. n is an integer from 0 to 20. q is an integer from 0 to 3. However, when R ¹³ and R ¹⁴ are each plural, a plurality of R ¹³ and R ¹⁴ are independent of each other.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a butyl group. From the viewpoint of easiness of hydrolysis, preferred among these are a methyl group and an ethyl group. From the viewpoint of carrying out the hydrolysis condensation reaction, the above q is preferably 1 or 2, more preferably 1.

In the case where the above R ¹⁴ is an alkyl group having 1 to 20 carbon atoms, the alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group or a third group. Butyl, n-pentyl. Preferred is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

Preferred among the (s2) compounds are a decane compound substituted with four hydrolyzable groups, a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, and more preferably one non-hydrolyzable. a decane compound substituted with three hydrolyzable groups. Particularly preferred hydrolyzable decane compounds include tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, methyl tributoxy decane, and phenyl. Trimethoxydecane, tolyltrimethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltributoxydecane, butyltrimethoxydecane And γ-glycidoxypropyltrimethoxydecane, naphthyltrimethoxydecane, γ-aminopropyltrimethoxydecane, and γ-isocyanatepropyltrimethoxydecane. These hydrolyzable decane compounds may be used singly or in combination of two or more.

Regarding the mixing ratio of the above (s1) compound and (s2) compound, it is preferred that the (s1) compound exceeds 5 mol%. When the amount of the (s1) compound is 5 mol% or less, there is a tendency that the exposure sensitivity at the time of forming the cured film is low, and the scratch resistance and the like of the obtained protective film are further lowered.

((s1) hydrolytic condensation of compound and (s2) compound)

When the (s1) compound and the (s2) compound are hydrolyzed and condensed, at least a part of the (s1) compound and the (s2) compound are hydrolyzed, and the hydrolyzable group is converted into a decyl group to cause a condensation reaction. There is no particular limitation, and as an example, it can be carried out as follows.

Examples of the solvent to be subjected to hydrolysis condensation include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol. Alcohol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like. These solvents may be used singly or in combination of two or more.

Preferred among the solvents are ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate. It is diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl methoxyacetate.

The hydrolysis condensation reaction is preferably carried out in the presence of a catalyst such as an acid catalyst, a base catalyst or an alkoxide.

The molecular weight distribution "Mw/Mn" of the hydrolysis-condensation product is preferably 3.0 or less, more preferably 2.6 or less. By setting the Mw/Mn of the hydrolysis condensate of the (s1) compound and the (s2) compound to 3.0 or less, the developability of the formed film can be improved. The radiation sensitive resin composition of the present embodiment containing polyoxyalkylene can easily form a desired pattern shape with less development of development residue during development.

[(D)Antioxidants]

The (D) antioxidant of the component (D) contained in the radiation sensitive resin composition of the present embodiment is a component that suppresses oxidation of the formed cured film.

As described above, the wiring included in the touch panel according to the first embodiment of the present invention includes a metal wiring including a first layer containing copper and an oxide containing the second metal element other than copper. The second layer formed by at least a part of the first layer. Therefore, when the cured film formed of the radiation sensitive resin composition of the present embodiment is used to cover the wiring of the touch panel, there is a metal oxide (for example, an oxide of manganese) on the surface of the wiring. And the concern of oxidation, which deteriorates. Therefore, the (D) antioxidant can be contained as the component (D) in the radiation sensitive resin composition of the present embodiment. The radiation-sensitive resin composition of the present embodiment contains (D) an antioxidant, and the cured film of the embodiment of the present invention formed by using the same is used as a film covering the wiring of the touch panel of the embodiment of the present invention. It can also suppress oxidation by using it, thereby suppressing deterioration.

The component (D) of the radiation-sensitive resin composition of the present embodiment may, for example, be a phenol-based antioxidant, a sulfur-based antioxidant or an amine-based antioxidant, and particularly preferably a phenol-based antioxidant.

Specific examples of the phenolic antioxidant include styrenated phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-t-butyl-p-ethylphenol, and 2 , 4,6-tri-tert-butylphenol, butyl hydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-tert-butyl-p-cresol, single third Base-m-cresol, 2,4-dimethyl-6-tert-butylphenol, butylated bisphenol A, 2,2'-methylene-bis-(4-methyl-6-third Butylphenol), 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis(4-methyl-6- Tridecylphenol), 2,2'-isobutylene-bis-(4,6-dimethylphenol), 4,4'-butylene-bis-(3-methyl-6-third Phenol), 4,4'-methylene-bis-(2,6-di-t-butylphenol), 2,2-thio-bis-(4-methyl-6-t-butyl Phenol), 4,4'-thio-bis-(3-methyl-6-tert-butylphenol), 4,4'-thio-bis-(2-methyl-6-butylphenol) 4,4'-thio-bis-(6-tert-butyl-3-methylphenol), bis(3-methyl-4-hydroxy-5-t-butylphenyl) sulfide, 2, 2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate], bis[3,3-bis(4'-hydroxy-3' - Tributylphenol) butyrate]diol, bis[2-(2-hydroxy-5-methyl-3-t-butylphenyl)-4-methyl-6-t-butylphenyl] Phthalate, 1,3,5- Tris(3',5'-di-t-butyl-4'-hydroxybenzyl)isocyanurate, N,N'-hexamethylene-bis(3,5-di-t-butyl -4-hydroxy-hydroxy decylamine), N-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol) propionate, tetrakis[methylene-( 3',5'-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,1'-bis(4-hydroxyphenyl)cyclohexane, mono(α-methylbenzyl) Phenol, bis(α-methylbenzyl)phenol, tris(α-methylbenzyl)phenol, bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4 -methyl-phenol, 2,5-di-third amyl hydroquinone, 2,6-di-butyl-α-dimethylamino-p-cresol, 2,5-di-third Butyl hydroquinone, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphoric acid, and the like.

These (D) antioxidants may be used singly or in combination of two or more.

The content of the (D) antioxidant is preferably 0.1 parts by mass to 10 parts by mass, based on 100 parts by mass of the total of the resin components contained in the radiation sensitive resin composition of the present embodiment. It is 0.2 parts by mass to 5 parts by mass.

[(E) Polyfunctional monomer]

The (E) polyfunctional monomer as the component (E) contained in the radiation-sensitive resin composition of the present embodiment is preferably contained together with the photopolymerization initiator as an example of the component (A) described above. . The radiation sensitive resin composition of the present embodiment can be suitably used as a radiation sensitive linear resin composition having a negative photosensitive property by containing a photopolymerization initiator as the component (A) and (E) a polyfunctional monomer. use.

The (E) polyfunctional monomer is preferably an allylated cyclohexyl di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, or 1,3-butanediol di(a) Acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(methyl) Acrylate, 1,10-nonanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol di(methyl) Acrylate, methoxycyclohexyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tripropyl Di(meth)acrylates such as triol di(meth)acrylate; pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide ( Propylene oxide, PO) modified tris(meth)acrylate, trimethylolpropane ethylene oxide (EO) modified tris(meth)acrylate, benzyl mercaptan tris(meth)acrylate a trifunctional or higher (meth) acrylate such as di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate or dipentaerythritol hexa(meth)acrylate; Wait a lot Energy (meth) acrylate.

In the radiation-sensitive resin composition of the present embodiment, the content of the (E) polyfunctional monomer is contained in the radiation-sensitive resin composition of the present embodiment from the viewpoint of sensitivity to light to be exposed. The total of 100 parts by weight of the resin component is preferably 10% by weight or more, and more preferably in the range of 50% by weight to 150% by weight.

[(F) Inorganic oxide particles]

The radiation sensitive resin composition of the present embodiment contains at least (A) a sensitizer, and (B) a compound containing an alkoxyalkyl group and at least a hydrolysis condensate of the compound. In addition to one, (F) inorganic oxide particles may be contained as an optional component.

The (F) inorganic oxide particles as the component (F) of the radiation sensitive resin composition of the present embodiment may be contained in the radiation sensitive resin composition, and the electrical insulation of the obtained cured product may be maintained and controlled as a dielectric. The relative dielectric constant of the characteristic. Further, the inorganic oxide particles can be used for the purpose of controlling the refractive index of the cured film, controlling the transparency of the cured film, suppressing cracking by relaxing the hardening shrinkage, and improving the surface hardness of the cured film.

The (F) inorganic oxide particles of the radiation sensitive resin composition of the present embodiment are inorganic oxide particles of an oxide selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, indium, and tin. An oxide of at least one element of the group consisting of ruthenium, osmium, iridium, osmium, and iridium.

Further, preferred in this group are oxide particles of cerium, zirconium, titanium or zinc, particularly preferably cerium oxide particles as cerium oxide particles, oxide particles of zirconium or titanium or strontium titanate ( BaTiO ₃ ). These may be used alone or in combination of two or more. Further, the (F) inorganic oxide particles may be composite oxide particles of the above elements. Examples of the composite oxide particles include barium titanate and barium titanate. Moreover, it is also possible to use antimony-tin oxide (ATO), indium-tin oxide (ITO), indium-zinc oxide (indium-zinc oxide) within a range that does not impair the electrical insulation of the cured product. , IZO) and so on. As such inorganic oxide particles, a commercially available person such as Nanotec (registered trademark) of CIKasei CO., LTD. can be used.

(F) The shape of the inorganic oxide particles is not particularly limited and may be spherical It may be amorphous, hollow particles, porous particles, core-shell particles, and the like. Further, the volume average particle diameter of the (F) inorganic oxide particles required for the dynamic light scattering method is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and particularly preferably 10 nm to 80 nm. When the volume average particle diameter of the (F) inorganic oxide particles is less than 5 nm, the hardness of the cured film obtained by using the radiation sensitive resin composition may be lowered or the desired relative dielectric constant may not be exhibited; When the thickness exceeds 200 nm, the haze of the cured film becomes high and the transmittance is lowered, or the smoothness of the cured film is deteriorated.

The amount of the inorganic oxide particles (F) is not particularly limited, and is preferably 1 part by mass based on 100 parts by mass of the total of the resin components contained in the radiation-sensitive resin composition of the present embodiment. ~500 parts by mass, more preferably 5 parts by mass to 300 parts by mass. When the amount of the inorganic oxide particles (F) is less than 1 part by mass, the above properties of the obtained cured film cannot be controlled within a desired range. On the other hand, when the amount of the inorganic oxide particles (F) is more than 500 parts by mass, the coating property or the film hardenability is lowered, and the haze of the obtained cured film is increased.

[(G) Solvents and other optional ingredients]

The radiation-sensitive resin composition of the present embodiment may contain (C) an alkali-soluble resin in addition to at least one of (A) a photosensitive agent, and (B) a compound containing an alkoxyalkyl group and a hydrolysis-condensation product of the compound. (D) an antioxidant, (E) polyfunctional monomer, and (F) inorganic oxide particle may further contain (G) a solvent and other arbitrary components.

When the radiation-sensitive resin composition of the present embodiment contains (F) inorganic oxide particles, it can be uniformly dispersed inside the radiation-sensitive resin composition by further containing a dispersant as the component (G) (F). The inorganic oxide particles can improve coatability. In addition, the radiation-sensitive resin composition of the present embodiment can improve the adhesion of the cured film obtained by using the cured film to the substrate or the like, and can be controlled so as to have a desired value similarly to characteristics such as a dielectric constant or a refractive index.

As such a dispersing agent, a dispersing agent described in JP-A-2011-128469 can be used.

The solvent of the component (G) is preferably one which can adjust the radiation-sensitive resin composition of the present embodiment to a desired solid content concentration, and the component (A) and the component (B) can be uniformly and stably. It is dissolved, and the component (C) or other optional component as the component (G) can be uniformly and stably dissolved. Further, when the radiation sensitive resin composition of the present embodiment contains (F) inorganic oxide particles, it is preferred that the (F) inorganic oxide particles be uniformly and stably dispersed in the radiation sensitive resin composition. In. Moreover, it is preferable to improve the coatability and film formability when the radiation sensitive resin composition of this embodiment is apply|coated on a board|substrate. In other words, the solvent of the component (G) is not particularly limited as long as it has the above functions.

(G) solvents such as methanol, ethanol, isopropanol, butanol, octanol and the like; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol Esters such as monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc. Ethers; decylamines such as dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl Ketones such as ketones; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. (G) The solvent may be used alone or in combination of two or more.

The surfactant of the component (G) can be added in order to improve the applicability of the radiation-sensitive resin composition of the present embodiment, to reduce coating unevenness, and to improve the developability of the radiation-irradiating portion. Examples of preferred surfactants include fluorine-based surfactants and anthrone-based surfactants. As such a surfactant, a dispersing agent described in JP-A-2011-128469 can be used.

The amount of the component to be used as the component (G) is preferably 0.01 parts by mass based on 100 parts by mass of the total of the resin components contained in the radiation sensitive resin composition of the present embodiment. ~10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass. By setting the amount of the surfactant to be 0.01 parts by mass to 10 parts by mass, the coating property of the radiation sensitive resin composition of the present embodiment can be optimized.

<Preparation of a radiation sensitive resin composition>

The radiation sensitive resin composition of the present embodiment can be mixed at a predetermined ratio by at least one of the above (A) photosensitive agent, and (B) alkoxyalkyl group-containing compound and a hydrolysis condensate of the compound. And prepared. Further, when the (C) alkali-soluble resin is contained, the component (A), the component (B) and the component (C) are mixed at a predetermined ratio.

Embodiment 3.

<Manufacture of cured film and touch panel>

In the method for producing a touch panel according to the third embodiment of the present invention, a step of forming a cured film using the radiation sensitive resin composition of the present embodiment described above is included as a main step. In the step of forming the cured film, patterning of the cured film is performed. Hereinafter, a step of forming a cured film as a main step will be mainly described, and a method of manufacturing the touch panel of the present embodiment will be described.

In the method of manufacturing a touch panel according to the present embodiment, in order to form a cured film on a substrate on which a detecting electrode, a wiring, or the like is disposed, it is preferable to include the following steps [1] to [3] in at least the following order. .

[1] Step of forming a coating film of the radiation sensitive resin composition of the second embodiment of the present invention

[2] a step of irradiating at least a part of the coating film formed in the step [1] with radiation

[3] Step of developing the coating film irradiated with radiation in the step [2]

Hereinafter, each step of the above [1] to [3] will be described.

[1] Step of forming a coating film of a radiation sensitive resin composition on a substrate

In the step [1], the radiation-sensitive resin composition of the second embodiment of the present invention is applied onto a substrate. Next, it is preferred to heat (pre-bake) the coated surface, and when the coating film contains a solvent, the solvent is removed to form a coating film.

The substrate is preferably a transparent substrate excellent in visible light transmittance. Examples of the substrate that can be used include a glass substrate, a resin substrate, and the like. Specific examples of the resin substrate include a polyethylene terephthalate film, a polybutylene terephthalate film, and polyethylene. A film, a polypropylene film, a polyether ruthenium film, a polycarbonate film, a polyacrylic acid film, a polyvinyl chloride film, a polyimide film, a ring-opening polymer film of a cyclic olefin, a film containing the hydride thereof, and the like.

Then, a detecting electrode and a wiring are formed on the substrate. The detecting electrode is formed by a known method. In other words, a transparent conductive film containing ITO or a transparent conductive film containing indium oxide and zinc oxide is formed on the glass substrate or the resin substrate by a known method, and then, if necessary, light micro-application can be used. The etching of the shadow method is formed.

Further, the wiring on the substrate can also be formed in accordance with the above method. In other words, the copper alloy is formed on the substrate by, for example, a plating method such as an electric field plating method or a dissolving plating method, or a physical vapor deposition method such as a vacuum deposition method or a sputtering method. Further, by using a known patterning method together with the method of forming a copper alloy, a wiring pattern including a copper alloy can be obtained, and by performing heat treatment, wiring can be formed on the substrate.

The coating method of the radiation sensitive resin composition is not particularly limited. For example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method can be employed. Particularly preferred among these coating methods is a spin coating method or a slit die coating method. The prebaking conditions vary depending on the type of each component, the blending ratio, etc., and it is preferably carried out at 70 ° C to 120 ° C for about 1 minute to 10 minutes.

[2] Step of irradiating at least a part of the coating film with radiation

In the step [2], at least a part of the coating film on the substrate formed in the step [1] is irradiated with radiation (hereinafter also referred to as "exposure"). In this case, for the film When a part of the exposure is performed, exposure is usually performed via a photomask having a predetermined pattern suitable for forming a cured film of the touch panel. As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The exposure amount in the step [2] is a value obtained by measuring the intensity of the radiation having a wavelength of 365 nm by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.), preferably 100 J/m ^{2 .} ~10000 J/m ² , more preferably 500 J/m ² to 6000 J/m ² .

[3] Development step

In the step [3], the exposed coating film obtained in the step [2] is developed to remove unnecessary portions (radiation in the case where the coating film of the radiation sensitive resin composition is positive) The irradiated portion is a non-irradiated portion of the radiation in the case of a negative type, and a predetermined pattern is formed.

As the developing solution used in the developing step, an alkaline developing solution containing an aqueous solution of an alkali (basic compound) is preferably used. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developing solution. The concentration of the alkali in the alkaline developing solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. The developing method can be, for example, a liquid coating method, a dipping method, or an oscillation method. A suitable method such as a dipping method or a shower method. The development time varies depending on the composition of the radiation-sensitive resin composition, and is preferably from about 10 seconds to about 180 seconds. Following such development processing, for example, a running water cleaning is performed for 30 seconds to 90 seconds, and then air-dried by, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

As described above, the cured film on the substrate formed by the steps [1] to [3] has high transparency and functions to protect the detecting electrode and the wiring.

Further, after the development in the step [3], the cured film may be further hardened by exposure as needed. Further, heat treatment at 80 ° C to 280 ° C may be performed instead of exposure after development, or heat treatment at 80 ° C to 280 ° C may be performed together with exposure. A cured film of higher strength is obtained as described above.

The film thickness of the cured film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, still more preferably 0.1 μm to 4 μm. The cured film formed of the radiation sensitive resin composition of the present invention is excellent in transparency, and has excellent adhesion to the substrate which can constitute the touch panel and the metal wiring formed on the substrate.

As described above, the detection electrode, the wiring, and the cured film are disposed on the light-transmitting substrate, whereby the touch panel of the embodiment of the present invention which exhibits high reliability can be manufactured.

[Examples]

Hereinafter, the embodiments of the present invention will be described in more detail based on the examples, but the present invention is not limited by the examples.

<Synthesis of alkoxyalkylalkyl-containing compound or its hydrolysis condensate >

Synthesis Example 1 (Synthesis of alkoxyalkylalkyl group-containing compound or hydrolysis condensate thereof (B-5))

20 parts by weight of propylene glycol monomethyl ether was placed in a container equipped with a stirrer, followed by 21 parts by weight of methyltrimethoxydecane (MTMS), 22 parts by weight of tetraethoxydecane (TEOS), and 3-propene oxide. 12 parts by weight of propyltrimethoxydecane (APTMS) and 4 parts by weight of 3-(trimethoxydecyl)propyl succinic anhydride (TMSPS) (MTMS/TEOS/APTMAS/TMSPS (Morby)=50/ 30/15/5), heating was carried out until the solution temperature became 60 °C. After the solution temperature reached 60 ° C, 0.1 part by weight of phosphoric acid and 20 parts by weight of ion-exchanged water were charged and heated to 75 ° C for 3 hours. Next, after cooling to 45 ° C, 29 parts by weight of methyl orthoformate was added as a dehydrating agent, and stirring was performed for 1 hour. Further, the solution temperature was set to 40 ° C, and evaporation was carried out while maintaining the temperature, whereby the ion exchange water and the methanol generated in the hydrolysis condensation were removed. From the above, a polyoxyalkylene (B-5) which is a hydrolysis condensate of a compound containing an alkoxyalkyl group is obtained. The obtained polyoxyalkylene (B-5) was in a state of a solution (polymer solution), and had a solid content concentration of 30% by weight, a polystyrene-equivalent weight average molecular weight (Mw) of 2,500, and a molecular weight distribution (dispersion) ( Mw/Mn) is 2.2.

<Synthesis of alkali soluble resin>

Synthesis Example 2 (Synthesis of alkali-soluble resin (C-1))

A flask having a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Then loaded with methyl 20 parts by weight of acrylic acid, 20 parts by weight of glycidyl methacrylate, 30 parts by weight of styrene, 30 parts by weight of N-cyclohexylmaleimide, and 7 parts by weight of α-methylstyrene dimer were subjected to nitrogen gas. After the replacement, slowly start stirring. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours, whereby a polymer solution containing the alkali-soluble resin (C-1) as a copolymer was obtained.

The solid content concentration of the polymer solution (the ratio of the weight of the polymer in the total weight of the polymer solution. The same applies hereinafter) was 31.0% by weight. Further, the alkali-soluble resin (C-1) had a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 and a molecular weight distribution (dispersion degree) (Mw/Mn) of 2.5.

Synthesis Example 3 (Synthesis of alkali-soluble resin (C-2))

Under dry nitrogen flow, bis(3-amino-4-hydroxyphenyl)hexafluoropropane (central glass (CENTRAL GLASS)) 29.30 g (0.08 mol), 1,3-bis (3-amino group) Propyl)tetramethyldioxane 1.24 g (0.005 mol), 3-aminophenol as a blocking agent (Tokyo Chemical Industry Co., Ltd.) 3.27 g (0.03 mol) dissolved in N-methyl-2- Pyrrolidone (hereinafter referred to as "NMP") was 80 g. 31.2 g (0.1 mol) of bis(3,4-dicarboxyphenyl)ether dianhydride (MANAC) and 20 g of NMP were added thereto, and reacted at 20 ° C for 1 hour, followed by 50 The reaction was carried out for 4 hours at °C. Thereafter, 15 g of xylene was added, and the water was azeotroped together with xylene, and stirred at 150 ° C for 5 hours. After the end of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80 ° C for 20 hours to obtain an alkali-soluble resin (C-2).

<Preparation of a radiation sensitive resin composition>

Example 1

To the polymer solution containing polyoxydecane (B-5) obtained in Synthesis Example 1 (100 parts by mass in terms of solid content), ethyl ketone as a component (A), 1-[9-ethyl-6 was added. -(2-Methylbenzylidene)-9H-indazol-3-yl]-, 1-(O-acetyl) (A-1) 3 parts by mass. Next, diethylene glycol ethyl methyl ether and methyl-3-methoxypropionate (the composition ratio was 30/70 (%)) were added so as to have a solid content concentration of 25% by weight to prepare a radiosensitivity. Composition.

Embodiment 2 to Embodiment 9

The component (A), the component (B), the component (C), the component (D), the component (E), and the component (F) as the inorganic oxide particles are used in the types and the amounts described in Table 1, respectively. A radiation sensitive resin composition of Examples 2 to 9 was prepared in the same manner as in Example 1 except the above.

Comparative Example 1 to Comparative Example 3

The feelings of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the components (A), (C) and (E) were used in the types and the amounts described in Table 1, respectively. A linear resin composition.

The compositions of the radiation sensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 are collectively shown in Table 1, and detailed representations of the respective components (A) to (F) are shown. In the following. In addition, "-" in the composition column of Table 1 indicates that a comparable component is not used. Further, in Table 1 and the following description, the component (B) is abbreviated as (B) a compound containing an alkoxyalkyl group or a hydrolysis-condensation product thereof.

(A) sensitizer

A-1: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetyl) (product Name: IRGACURE (registered trademark) OX02, manufactured by BASF)

A-2: 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile ("CGI-725" by BASF Corporation)

A-3: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

(B) a compound containing an alkoxyalkyl group or a hydrolyzed condensate thereof

B-1: 3-glycidoxypropyltrimethoxydecane (trade name: Sila-Ace (registered trademark) S510, manufactured by JNC Corporation)

B-2: 3-isocyanate propyl trimethoxy decane (trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.)

B-3: 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine (trade name: KBE-9103, manufactured by Shin-Etsu Chemical Co., Ltd.)

B-4: Hydrolyzed condensate of γ-methacryloxypropyltrimethoxydecane

B-5: MTMS/TEOS/APTMS/TMSPS=50/30/15/5 mol% hydrolysis condensate

(C) alkali soluble resin

C-1: methacrylic acid/glycidyl methacrylate/styrene/N-cyclohexylmaleimide=20/20/30/30 wt% copolymer obtained in Synthesis Example 2

C-2: Resin obtained in Synthesis Example 3

(D) Antioxidants

D-1: thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX (registered trademark) 1035, manufactured by Ciba Specialty Chemicals Co., Ltd.)

D-2: pentaerythritol = tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX (registered trademark) 1010, steam Made by Ba Jinghua Co., Ltd.)

D-3: tris(2,4-di-t-butylphenyl)phosphite (trade name: Adekastab (registered trademark) 2112, manufactured by ADEKA)

(E) polyfunctional monomer

E-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Morby 50/50) (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(F) inorganic oxide particles

F-1: ZrO ₂ sol (trade name: ID191, manufactured by Tayca Co., Ltd.)

<Evaluation of cured film>

Example 10

Using the radiation sensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3, a cured film was formed as described below, and the properties were evaluated and compared.

Table 1 to Example 9 and Comparative Example 1 to Comparative Example 3 are shown in Table 1. The composition of the radiation sensitive resin composition prepared in the above, and collectively shows the evaluation results of the cured film produced using these.

[Evaluation of Transmittance and Heat Resistance Transparency]

The radiation sensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were applied to a glass substrate ("Corning 7059" (manufactured by Corning Incorporated)) using a spin coater, and then The coating film was formed by prebaking on a hot plate at 90 ° C for 2 minutes. Next, exposure was carried out using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd., and development was carried out using a 0.4% by mass aqueous solution of tetramethylammonium hydroxide. Further, heating was carried out at 230 ° C for 30 minutes, whereby a cured film having a film thickness of 2.0 μm was obtained. The glass substrate on which the cured film was formed was measured for a light transmittance in a wavelength range of 400 nm to 800 nm using a spectrophotometer "150-20 double beam photometer" (manufactured by Hitachi, Ltd.). Regarding each glass substrate, the lowest value (also referred to as "lowest transmittance") of the light transmittance in the range of 400 nm to 800 nm was evaluated. Further, the light transmittance at a wavelength of 400 nm was used as an evaluation criterion, and when the light transmittance at a wavelength of 400 nm was 85% or more, it was determined that the light transmittance characteristics were particularly good.

The evaluation result is shown as "transmittance (%)" and is collectively shown in Table 1 which will be described later. Further, the substrate on which each of the cured films was formed was heated in a clean oven at 250 ° C for 3 hours, and a spectrophotometer (150-20 type double beam photometer manufactured by Hitachi, Ltd.) was used. On the other hand, the light transmittance (%) of the wavelength of 400 nm before and after heating was measured, and "heat-resistant transparency (%)" was calculated according to the following formula. When the value is 10% or less, it is judged that the heat resistance of the protective film Good transparency.

Heat-resistant transparency (%) = light transmittance before heating (%) - light transmittance after heating (%)

The cured film obtained by using the radiation sensitive resin composition prepared in Examples 1 to 9 was particularly excellent in heat-resistant transparency at a wavelength of 400 nm of 10% or less. The cured film obtained by using the radiation-sensitive resin composition prepared in Comparative Example 1 to Comparative Example 3 had a heat-resistant transparency at a wavelength of 400 nm of 10% or more, and did not obtain good heat-resistant transparency.

[Adhesiveness and Evaluation of Adhesion after Pressure Cooker Test (PCT)]

A copper-manganese alloy was produced by the method described in Japanese Patent No. 4,453,845, and the obtained copper-manganese alloy was sputtered on a glass substrate ("Corning 7059" (manufactured by Corning)) as a sputtering target. Heating is performed to obtain a substrate on which a metal electrode is formed. The radiation sensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were applied onto the substrate by a spin coater, and then dried on a hot plate at 90 ° C for 2 minutes. Pre-baking to form a coating film. Next, exposure was carried out using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd., and development was carried out using a 0.4% by mass aqueous solution of tetramethylammonium hydroxide. Further, heating was carried out at 230 ° C for 30 minutes, whereby a cured film having a film thickness of 2.0 μm was obtained.

Pressure cooker test on the substrate on which the cured film is formed (120 ° C, wet Degree 100%, 4 hours). The substrate before and after the pressure cooker test was subjected to "8.5.3 Adhesive Mesh Tape Method of JIS K-5400-1990", and the number of meshes remaining in 100 meshes was determined, and the adhesion of each cured film was evaluated. Further, the evaluation results of the substrate before the pressure cooker test are summarized in Table 1 as "adhesiveness" of each cured film. In addition, the evaluation results of the substrate after the pressure cooker test are summarized in Table 1 as "adhesiveness after PCT" of each cured film. In the evaluation of the adhesion after PCT, when the number of meshes remaining in 100 meshes is 80 or less, the adhesion after PCT is judged to be defective.

The adhesion after PCT of the cured film obtained by using the radiation-sensitive resin composition prepared in each of Examples 1 to 9 was good in the number of meshes remaining in 100 meshes of 80 or more. The cured films obtained by using the radiation-sensitive resin compositions prepared in Comparative Examples 1 to 3 were 20 and 0, respectively, and were all inferior.

<Manufacture and evaluation of touch panel>

Example 11

In the present embodiment, a touch panel having the same structure as that of the touch panel 21 of the present embodiment illustrated in FIG. 1 was manufactured and evaluated. In the touch panel of the present embodiment, the components common to the touch panel of FIG. 1 are denoted by the same reference numerals, and the description will be made with reference to FIG. 1 and the like as appropriate.

As shown in FIG. 1 , the touch panel 21 manufactured in the present embodiment includes an operation area of 3 cm in length × 3 cm in width on the transparent substrate 22, and each of the three rows of films is included in the film. The first detecting electrode 23 extending in the X direction and the second detecting electrode 24 extending in the Y direction orthogonal to the X direction are formed by ITO having a thickness of 30 nm.

In the manufacture of the touch panel 21, the transparent substrate 22 is first prepared. As the transparent substrate 22, a 0.55 mm thick glass substrate as an alkali-free glass was used, and surfactant treatment was performed using ultrapure water, followed by washing by ultrasonic cleaning.

Next, a wiring 31 as a metal wiring is formed on the transparent substrate 22. First, a copper-manganese alloy was produced by the method described in Japanese Patent No. 4,453,845, and the prepared copper-manganese alloy was used as a sputtering target on the transparent substrate 22 by sputtering at a thickness of 30 nm. A metal film containing a copper-manganese alloy is formed. Then, using a positive photosensitive material, a pattern of a wiring including a copper alloy is formed by a photolithography method in a wiring region other than the operation region. Next, the wiring pattern on the transparent substrate 22 was heat-treated at 300 ° C for 5 minutes in an air atmosphere using an oven to form a second layer containing a copper-manganese alloy and a second layer containing manganese. Wiring 31.

Next, in order to form the first detecting electrode 23 and the second detecting electrode 24 on the transparent substrate 22 on which the wiring 31 is formed, an ITO film is formed on the entire surface by a sputtering method at a thickness of 30 nm. Then, the first detecting electrode 23 and the second detecting electrode 24 are formed by photolithography using the same positive photosensitive material as when the wiring 31 is formed.

4 is a plan view showing a wiring, a first detecting electrode, and a second detecting electrode formed on a transparent substrate in order to form a touch panel.

As shown in FIG. 4, the first detecting electrode 23 and the second detecting electrode 24 are respectively Four electrode pads 30 including a diamond shape are included. Further, in the intersection portion 28 where the first detecting electrode 23 and the second detecting electrode 24 intersect, the first detecting electrode 23 is connected, and the second detecting electrode 24 is formed to be disconnected.

Next, an acrylic resin material (manufactured by JSR Corporation, No. NN902) was used to form a coating film on the transparent substrate 22 on which the wiring 31, the first detecting electrode 23, and the second detecting electrode 24 were formed by a spin coating method. Next, heating (prebaking) was performed on a hot plate at 90 ° C for 45 seconds to remove the solvent component. After the substrate was cooled to room temperature, a mask having a mask pattern was formed using the interlayer insulating layer 29, and a exposure amount of 100 mJ at 365 nm was performed by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc. Perform exposure processing. Next, an inorganic alkali solution (CD150-CR manufactured by JSR Corporation) was used as a developing solution to perform immersion development, and the unexposed portion was removed, and thereafter, a pattern of the interlayer insulating layer 29 was formed. In addition, the pattern formed on the transparent substrate 22 is cured by heating (post-baking) in an oven at 230 ° C for 1 hour in an atmosphere, and a film is formed on the first detecting electrode 23 of the intersection portion 28 . A patterned interlayer insulating layer 29 having a thickness of 1.5 μm.

Next, in order to electrically connect the discontinuous portion of the second detecting electrode 24 to the interlayer insulating layer 29, the bridge wiring 32 is formed on the interlayer insulating layer 29 of the intersecting portion 28. Specifically, first, ITO was used to form the bridge wiring 32, and a film was formed on the entire surface of the substrate by a sputtering method at a thickness of 50 nm. Then, a positive photosensitive material is used in the same manner as the first detecting electrode 23, and the ITO film is patterned by photolithography to form a plurality of layers on the interlayer insulating film 29 of the intersection portion 28 of the touch panel 21. Bridge wiring 32.

5 is a plan view showing a wiring, a first detecting electrode, a second detecting electrode, an interlayer insulating layer, and a bridge wiring formed on a transparent substrate in order to form a touch panel.

As shown in FIG. 4, the first detecting electrode 23 is connected to the intersection portion 28 on the transparent substrate 22, and the second detecting electrode 24 is formed to be broken. Therefore, in order to electrically connect the portion where the second detecting electrode 24 is interrupted, the bridge wire 32 is provided. An interlayer insulating film 29 is provided between the bridge wiring 32 and the first detecting electrode 23.

Next, the radiation-sensitive resin composition prepared in the above Example 5 was applied to the entire surface of the substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating. membrane. The radiation-sensitive resin composition of Example 5 is a polymer solution containing an alkali-soluble resin (C-1) obtained in Synthesis Example 2 in the same manner as in the above Example 1 (solid content is 100 parts by mass) Ethyl ketone as component (A), 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine) (3) parts by mass of (A-1), 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine (B-3) 10 as a component (B) 3 parts by weight of thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (D-1) as a component (D), 100 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Mole ratio 50/50) (E-1) as a component (E), and then added as a solid content concentration of 25% by weight. Prepared by diethylene glycol ethyl methyl ether and methyl-3-methoxypropionate (composition ratio is 30/70 (%)).

Next, it is preferable to use a photomask having a mask pattern formed by the cured film 25. The PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Nippon Co., Ltd. was exposed, and developed using a 0.4% by mass aqueous solution of tetramethylammonium hydroxide. Further, the film was heated at 230 ° C for 30 minutes to form a cured film 29 having a film thickness of 2.0 μm, whereby the touch panel 21 of the present embodiment having the same configuration as that of FIG. 1 was obtained.

Next, the touch panel 21 of the present embodiment was used and placed in a high-temperature and high-humidity bath having a temperature of 85 ° C and a humidity of 85%, and taken out after 240 hours, and the peeling between the wiring 31 and the cured film 25 was evaluated. Whether there is. As a result, in the touch panel 21 of the present embodiment, peeling does not occur between the wiring 31 and the cured film 25, and the adhesion between the wiring 31 and the cured film 25 is good, and excellent reliability is obtained.

The present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit and scope of the invention.

[Industrial availability]

The touch panel of the present invention has high reliability. Therefore, the touch panel of the present invention is suitable as an input device for a portable information device that requires excellent display quality and reliability.

21‧‧‧ touch panel

22‧‧‧Transparent substrate

23‧‧‧1st detecting electrode

24‧‧‧2nd detection electrode

25‧‧‧hard film

28‧‧‧Intersection

29‧‧‧Interlayer insulating film

30‧‧‧electrode pads

31‧‧‧Wiring

32‧‧‧Bridge wiring

Claims (20)

A touch panel comprising a metal wiring and a cured film covering at least a part of the metal wiring, wherein the metal wiring is a metal wiring including a second metal element other than copper or copper. The cured film is formed by using a radiation-sensitive resin composition containing (A) a photosensitive agent, and (B) a compound containing an alkoxyalkyl group and hydrolysis condensation of the compound At least one of the things. The touch panel according to claim 1, wherein the metal wiring includes a first layer containing copper, an oxide including the second metal element, and covering at least a portion of the first layer The metal wiring of the second layer formed in this manner. The touch panel of claim 1 or 2, wherein the second metal element is selected from the group consisting of lithium, lanthanum, cerium, tin, lanthanum, cerium, lanthanum, phosphorus, manganese, magnesium, calcium. At least one of a group consisting of nickel, zinc, lanthanum, aluminum, lanthanum, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium. The touch panel of claim 1 or 2, wherein the second metal element is manganese. The touch panel according to the first or second aspect of the invention, wherein the cured film is formed by using a radiation sensitive resin composition further containing (C) an alkali-soluble resin. The touch panel of claim 5, wherein the component (C) of the radiation sensitive resin composition comprises a carboxyl group selected from the group consisting of At least one of the group consisting of acrylic resin, polyamine, and polyoxyalkylene. The touch panel according to claim 1 or 2, wherein the cured film is formed by using a radiation sensitive resin composition further containing (D) an antioxidant. The touch panel of claim 1 or 2, wherein the cured film is further used to contain (F) as comprising an element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, indium, tin, antimony. The radiation-sensitive resin composition of the inorganic oxide particles of the oxide of at least one element of the group consisting of ruthenium, osmium, iridium and osmium is formed. The touch panel according to the first or second aspect of the invention, wherein the component (A) of the radiation sensitive resin composition contains at least one of a photoacid generator and a photopolymerization initiator. The touch panel according to claim 1 or 2, wherein the component (B) of the radiation sensitive resin composition comprises an amine group, a block amine group, an isocyanate group, and a blocked isocyanate group. At least one of the compounds. A radiation-sensitive resin composition comprising at least one of (A) a photosensitive agent, and (B) a compound containing an alkoxyalkyl group and a hydrolysis condensate of the compound; a cured film for forming a touch panel, the touch panel comprising a metal wiring and the cured film covering at least a portion of the metal wiring, the metal wiring comprising a first layer comprising copper, And a second layer comprising an oxide of a second metal element other than copper and covering at least a part of the first layer. The radiation sensitive resin composition according to claim 11, which further comprises (C) an alkali-soluble resin. The radiation sensitive resin composition according to claim 12, wherein the component (C) comprises at least one selected from the group consisting of an acrylic resin having a carboxyl group, a polyamine, and a polyoxyalkylene. The radiation-sensitive resin composition according to any one of the preceding claims, wherein the oxide of the second metal element contained in the second layer of the metal wiring is selected Free lithium, antimony, bismuth, tin, antimony, bismuth, antimony, phosphorus, manganese, magnesium, calcium, nickel, zinc, antimony, aluminum, antimony, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium An oxide of at least one element of the group. The radiation sensitive resin composition according to any one of claims 11 to 13, which further comprises (D) an antioxidant. The radiation sensitive resin composition according to any one of the items 11 to 13, which further comprises (E) a polyfunctional (meth) acrylate. The radiation sensitive resin composition according to any one of claims 11 to 13, which further comprises (F) as comprising an element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, indium, tin, antimony. Inorganic oxide particles of an oxide of at least one element of the group consisting of ruthenium, osmium, iridium and osmium. The radiation sensitive resin composition according to any one of the items 11 to 13, wherein the component (A) comprises a photoacid generator and a photopolymerization initiation At least one of the agents. The radiation-sensitive resin composition according to any one of the preceding claims, wherein the component (B) comprises at least an amine group, a block amine group, an isocyanate group, and a blocked isocyanate group. a compound of one. A cured film formed of a radiation sensitive resin composition comprising at least one of (A) a photosensitive agent, and (B) a compound containing an alkoxyalkyl group and a hydrolysis condensate of the compound; The cured film is characterized by covering at least a part of the metal wiring of the touch panel including the metal wiring, the metal wiring including a first layer containing copper and an oxide containing a second metal element other than copper And a second layer configured to cover at least a part of the first layer.