JP2017090588A - Liquid crystal display element and radiation-sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display element with a built-in touch sensor function that can be easily formed and has an interlayer insulating film with easily controllable dielectric properties, and to provide a radiation-sensitive resin composition forming the interlayer insulating film.SOLUTION: A pixel 30 of a liquid crystal display element 10 includes: a first layer 34, having a TFT 33 and a first common wiring 15-1 on a surface of a first substrate 31 near a liquid crystal layer 32, a second layer 35, having a second common wiring 17-1 and a common electrode 12, and a third layer 38, having a pixel electrode 36 and an interlayer insulating film 37. The interlayer insulating film 37 is an organic film formed using a radiation-sensitive resin composition. In image display, a common voltage is supplied to the common electrode 12 using the second common wiring 17-1. At the usage of the touch sensor function, a change in the capacity between the first common wiring 15-1 and the second common wiring 17-1 is detected so that a touch is detected.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a liquid crystal display element and a radiation sensitive resin composition.

  In recent years, in electronic devices such as smartphones, tablet PCs, notebook PCs, OA devices, and car navigation systems, touch sensors configured as panels and touch panels that are arranged on the substrate as touch devices are used as input devices on their displays. Is actively used.

  The touch sensor and the touch panel can be operated with an electronic device by touching the surface with an operator's finger or pen and outputting data related to the touch operation to various processing devices. For example, a touch panel can be used as an input device that replaces a keyboard, and enables easy input of information in an interactive manner in the electronic device described above.

  The touch sensor and the touch panel include a resistance film method, a capacitance method, an infrared method, an ultrasonic method, and an electromagnetic inductive coupling method depending on the operation principle.

  In such a touch sensor or touch panel, for example, a plurality of first detection electrodes extending in a predetermined first direction and a plurality of second detection electrodes extending in a second direction intersecting with the first detection electrodes, as in a capacitance method, are used. Are combined and arranged on an insulating transparent substrate such as glass.

  FIG. 4 is a plan view schematically showing an example of a conventional touch panel.

  A conventional touch panel 100 shown in FIG. 4 has a plurality of strip-shaped first detection electrodes that extend in one direction, the X direction (the horizontal direction in the drawing), on one surface of an insulating transparent substrate 101. 102, a plurality of strip-shaped second detection electrodes 104 extending in the Y direction (vertical direction in the drawing) in a second direction orthogonal to the first direction, a plurality of first detection electrodes 102, and a plurality of first detection electrodes 2 and an interlayer insulating film 105 provided between the sensing electrodes 104.

  That is, the conventional touch panel 100 includes a plurality of first detection electrodes 102, an interlayer insulating film 105, and second detection electrodes 104 arranged in this order from the substrate 101 side on one surface of the transparent substrate 101. It has a structure. The second detection electrode 104 is disposed so as to overlap the first detection electrode 102 via the interlayer insulating film 105 and intersect the first detection electrode 102. The intersection between the first detection electrode 102 and the second detection electrode 104 is configured to ensure insulation by the interlayer insulating film 105.

  In the conventional touch panel 100, the capacitance is measured by using the first detection electrode 102 and the second detection electrode 104 as a touch sensor, and the change of the capacitance caused by the touch operation of the operator's finger or the like is used. The position can be detected.

  Conventionally, such a touch panel has been used by being mounted on the front side of a display panel such as a liquid crystal display panel manufactured separately. For example, a liquid crystal display element is configured using a liquid crystal display panel and a touch panel externally attached thereto. The conventional liquid crystal display element is configured such that an information input operation can be performed by touching the touch panel on the surface with a finger or a pen together with displaying an image and sensing the touch operation.

  However, in the conventional liquid crystal display element, since a touch panel manufactured as a separate body is externally attached to the outside of the display panel, the thickness and weight of the entire element increase, and the manufacturing cost increases. Had.

  For this reason, recently, for example, as a touch screen described in Patent Document 1, a built-in touch panel is configured by incorporating a touch sensing circuit constituting a touch sensor inside a display panel such as a liquid crystal display panel. Development is actively underway. By incorporating the touch sensor function, the thickness and weight of the entire display element can be reduced compared to an external touch panel. And the process for attaching a touch panel externally can be omitted, and the manufacturing cost of the display element can be reduced.

JP 2010-231773 A

  As described above, since the display element has a built-in touch sensor function, an increase in thickness and weight of the entire display element can be suppressed, and a manufacturing cost can be reduced. The display element can have both an image display function and a touch sensor function.

  However, recently, for display elements having such a touch sensor function, further simplification of manufacturing processes and cost reduction have been demanded.

  For example, in the case of the touch screen described in Patent Document 1 described above, in a display panel constituting the touch screen, pixel electrodes for image display are arranged on a substrate, and common electrodes for image display are arranged on the same substrate. Has been placed. An insulating interlayer insulating film is disposed between the pixel electrode and the common electrode, and the pixel electrode is configured to face the common electrode through the interlayer insulating film.

  In the touch screen display panel described in Patent Document 1, a substrate having a pixel electrode and a common electrode constitutes a liquid crystal display panel by sandwiching a liquid crystal layer between the pixel electrode and the common substrate.

  Therefore, the touch screen described in Patent Document 1 has an image display function using the liquid crystal layer of the liquid crystal display panel. In the touch screen liquid crystal display panel, the image display common electrode is configured to function as a detection electrode for detecting a touch.

  In such a conventional touch screen liquid crystal display panel, an inorganic film made of SiN (silicon nitride) is usually used as an interlayer insulating film disposed between the pixel electrode and the common electrode. This inorganic film made of SiN can be formed by CVD (Chemical Vapor Deposition).

  Therefore, in the case of the prior art such as the touch screen described in Patent Document 1, it is usual to provide a CVD process for the configuration of the interlayer insulating film between the pixel electrode and the common electrode of the liquid crystal display panel. Therefore, in the prior art, a manufacturing apparatus used for the manufacturing has been large-scale. In order to improve productivity, if a large substrate is to be used, an increasingly large manufacturing apparatus is required.

  Therefore, in the conventional technology such as the touch screen described in Patent Document 1, a technology that further simplifies the manufacturing process and enables cost reduction is required.

  For example, in the prior art as described above, a technique for simplifying the formation of an interlayer insulating film disposed between the pixel electrode and the common electrode is required. That is, there is a need for an interlayer insulating film that can be easily formed on a large substrate without requiring a large-scale manufacturing apparatus for CVD or the like.

  An interlayer insulating film that can be easily formed is excellent in patterning properties, and preferably has excellent insulating properties and light transmission characteristics as in the case of conventional interlayer insulating films. Further, the interlayer insulating film preferably has the same dielectric characteristics and refractive index characteristics as those of the conventional interlayer insulating film. In particular, it is preferable that the interlayer insulating film can have the same dielectric characteristics as the interlayer insulating film made of SiN so as to be easily replaced with the conventional interlayer insulating film made of SiN.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a liquid crystal display element having an interlayer insulating film which can be easily formed and whose dielectric characteristics can be easily controlled, and which incorporates a touch sensor function.

  Another object of the present invention is to provide a radiation-sensitive resin composition that can easily control dielectric characteristics and is used for forming an interlayer insulating film of a liquid crystal display element incorporating a touch sensor function.

The first aspect of the present invention is:
A liquid crystal layer is sandwiched between a first substrate and a second substrate which are arranged to face each other, and a plurality of pixels arranged in a matrix form in a display region, and an image display function and a touch sensor function for sensing touch With respect to a liquid crystal display device comprising
At least some of the plurality of pixels are
On the liquid crystal layer side of the first substrate,
A first layer including a TFT and a first common wiring;
A second layer including a second common wiring and a common electrode connected to the second common wiring;
A pixel electrode connected to the TFT and an interlayer insulating film, the pixel electrode having a third layer having a structure facing the common electrode via the interlayer insulating film in this order;
The interlayer insulating film is an organic film;
When the image display function is used, a common voltage is supplied to the common electrode of the pixel using the second common wiring,
The liquid crystal is configured to sense the touch by sensing a change in capacitance between the first common wiring and the second common wiring when the touch sensor function is used. The present invention relates to a display element.

In the first aspect of the present invention, the interlayer insulating film comprises:
[A] polymer,
[B] a photosensitive agent, and [C] a radiation-sensitive resin composition comprising a compound containing titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium, and lead. It is preferable that it is formed using.

  1st aspect of this invention WHEREIN: It is preferable that the said interlayer insulation film is formed using the said radiation sensitive resin composition, and [A] polymer is a polymer containing the structural unit which has a carboxyl group.

  In the first aspect of the present invention, the interlayer insulating film is formed using the radiation-sensitive resin composition, and [B] the photosensitive agent is at least selected from a photoradical polymerization initiator and a photoacid generator. It is preferable to include one.

  In the first aspect of the present invention, the interlayer insulating film is formed using the radiation-sensitive resin composition, and the [C] compound has a particle diameter in the range of 0.01 μm to 0.1 μm, and c / The a-axis ratio is preferably 1.0025 to 1.010.

  1st aspect of this invention WHEREIN: It is preferable that the said interlayer insulation film is formed using the said radiation sensitive resin composition, and a [C] compound is barium titanate.

  In the first aspect of the present invention, the interlayer insulating film is formed using the radiation-sensitive resin composition, and the radiation-sensitive resin composition further includes at least one of [D] urethane bond and amide bond. It is preferable to include at least one selected from the group consisting of a polymer having one and a (meth) acrylate compound having at least one of a urethane bond and an amide bond.

  The liquid crystal display element of the first aspect of the present invention is preferably an FFS mode liquid crystal display element.

The second aspect of the present invention is:
[A] polymer,
[B] a photosensitive agent, and [C] a radiation-sensitive resin composition comprising a compound containing titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium, and lead. Because
The present invention relates to a radiation-sensitive resin composition, which is used for forming an interlayer insulating film of the liquid crystal display element according to the first aspect of the present invention.

  2nd aspect of this invention WHEREIN: It is preferable that a [A] polymer is a polymer containing the structural unit which has a carboxyl group.

  In the second aspect of the present invention, it is preferable that the [B] photosensitizer contains at least one selected from a photo radical polymerization initiator and a photo acid generator.

  In the second embodiment of the present invention, the [C] compound preferably has a particle diameter in the range of 0.01 μm to 0.1 μm and a c / a axial ratio of 1.0025 to 1.010.

  In the second aspect of the present invention, the [C] compound is preferably barium titanate.

  In the second embodiment of the present invention, it further comprises [D] a polymer having at least one of a urethane bond and an amide bond, and a (meth) acrylate compound having at least one of a urethane bond and an amide bond. It is preferable to include at least one selected from the group.

  According to the first aspect of the present invention, a liquid crystal display element having an interlayer insulating film that can be easily formed and whose dielectric characteristics can be easily controlled and that has a built-in touch sensor function can be obtained.

  According to the second aspect of the present invention, it is possible to obtain a radiation-sensitive resin composition that can be easily controlled in dielectric properties and used for forming an interlayer insulating film of a liquid crystal display element incorporating a touch sensor function.

1 is a schematic plan view illustrating an example of a display region of a liquid crystal display element that is a first embodiment of the present invention. It is sectional drawing which shows typically a part of structure of the pixel of the sensing region of a display area | region of the liquid crystal display element which is 1st Embodiment of this invention. It is sectional drawing which shows typically a part of pixel structure of the drive region of a display area | region of the liquid crystal display element which is 1st Embodiment of this invention. It is a top view which shows typically an example of the conventional touch panel.

  In the case of a touch screen with a built-in touch sensor function disclosed in Patent Document 1, a liquid crystal display panel constituting the touch screen has a pixel electrode for image display on a substrate. In the liquid crystal display panel, a common electrode to which a common voltage is supplied is arranged on the same substrate so as to face the pixel electrode through an interlayer insulating film. As described above, the common electrode is used for image display together with the pixel electrode in the liquid crystal display panel of the touch screen, and also functions as a detection electrode for detecting a touch.

  That is, in a conventional touch screen liquid crystal display panel, an interlayer insulating film is provided between a pixel electrode and a common electrode which are arranged on the same substrate so as to ensure insulation between them. As the interlayer insulating film, an interlayer insulating film made of an inorganic material such as SiN (hereinafter also simply referred to as an inorganic interlayer insulating film) is usually used. Since this inorganic interlayer insulating film is formed by a film forming method such as CVD, a large-scale manufacturing apparatus is required.

  In order to realize such an interlayer insulating film that can be formed by a simple method in place of such an inorganic interlayer insulating film, an organic film formed using an organic material, which is a coating type interlayer insulating film Is preferable.

  If a coating-type interlayer insulating film made of such an organic material is used and a conventional inorganic interlayer insulating film made of SiN or the like can be substituted, a simple interlayer insulating film can be formed. That is, similar to the touch screen described in Patent Document 1 and the like described above, a simple interlayer insulating film can be formed in a liquid crystal display element incorporating a touch sensor function. Furthermore, it becomes easy to apply a large substrate, and the productivity of a liquid crystal display element incorporating a touch sensor function can be improved.

  Therefore, an alternative to a conventional inorganic interlayer insulating film by an interlayer insulating film that is an organic film (hereinafter also simply referred to as an organic interlayer insulating film) is considered.

  However, in order to realize such an alternative to the conventional inorganic interlayer insulating film, the organic interlayer insulating film is strongly required to have insulating properties, patterning properties, light transmittance, and the like. Therefore, it is preferable that the organic interlayer insulating film can be formed using a liquid radiation-sensitive resin composition that can be patterned and using a coating method or the like.

  Furthermore, the organic interlayer insulating film that can replace the inorganic interlayer insulating film preferably has the same dielectric characteristics and refractive index characteristics as those of the conventional inorganic interlayer insulating film. In particular, it is preferable that the organic interlayer insulating film has the same characteristics as the conventionally used inorganic interlayer insulating film made of SiN and can be used in the same manner. Therefore, it is preferable that the organic interlayer insulating film can be controlled so that the capacitance C is equal to or more than or less than that of the inorganic interlayer insulating film made of SiN.

At this time, the capacitance C of the interlayer insulating film considered can be expressed by C = ε × (S / d). Here, ε is a dielectric constant of a member constituting the interlayer insulating film. S is the area of the member, and can be, for example, the area of the electrode effective for C formation. d is the thickness of the member, and in the case of an interlayer insulating film, it is the film thickness. Ε is expressed by ε = ε ₀ × k. At this time, ε ₀ is a dielectric constant in vacuum and is a constant. k is a relative dielectric constant of the member, and is a value specific to the member.

  The relative dielectric constant k of SiN that has been used in conventional inorganic interlayer insulating films is about 6 to 7, that is, 6 to 7, and the relative dielectric constant of a resin such as ethylene resin or acrylic resin is 2 or more and 4 or less. That is, it has a large value compared with 2-4. Therefore, when the interlayer insulating film is to be an organic interlayer insulating film using a resin composition, the relative dielectric constant of the component is set so that the capacitance is equal to or higher than that of the inorganic interlayer insulating film made of SiN. Increased control is required. At the same time, it is required to maintain insulating properties and realize good patterning properties.

  Therefore, the present inventor can apply a technique for increasing the relative dielectric constant of the constituent components to control the dielectric constant to a desired value, for example, can be controlled to be the same as a conventional inorganic interlayer insulating film made of SiN. Developed an organic film. And the technique which uses the organic film as an interlayer insulation film of a liquid crystal display element was developed.

  And the interlayer insulation film of this invention can have a high refractive index compared with the organic film using the conventional organic material. The interlayer insulating film of the present invention can have a refractive index similar to that of a conventional inorganic interlayer insulating film made of SiN, for example. Since the interlayer insulating film of the present invention has such a refractive index characteristic, in the liquid crystal display element incorporating the touch sensor function of the present invention, the detection electrode is conspicuous on the screen. The problem can be reduced.

  The interlayer insulating film of the present invention can be easily formed by coating using a radiation-sensitive resin composition and can be patterned as desired.

  Therefore, the interlayer insulating film of the present invention can replace the conventional inorganic interlayer insulating film made of SiN, and is disposed between the pixel electrode and the common electrode, and is a liquid crystal display element incorporating the touch sensor function of the present invention. It can be provided.

  Hereinafter, the liquid crystal display element of the present invention having the interlayer insulating film of the present invention provided in place of the conventional inorganic interlayer insulating film, and the radiation-sensitive resin composition of the present invention for forming the interlayer insulating film will be described. To do.

  In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

Embodiment 1 FIG.
<Liquid crystal display element>
FIG. 1 is a schematic plan view showing an example of a display area of a liquid crystal display element according to the first embodiment of the present invention.

  The liquid crystal display element 10 according to the first embodiment of the present invention is configured such that a liquid crystal layer (not shown) is sandwiched between a first substrate (not shown) and a second substrate (not shown) arranged to face each other. The The liquid crystal display element 10 has a plurality of pixels arranged in a matrix in the display region 11. In FIG. 1, the display area 11 is schematically shown as an area surrounded by a one-dot chain line. Moreover, in FIG. 1, only the common electrode 12 which comprises the pixel is typically shown by the part corresponding to each pixel.

  As described above, the display area 11 of the liquid crystal display element 10 includes a plurality of pixels arranged in a matrix and is an area for displaying an image. As shown in FIG. 1, in the liquid crystal display element 10, the display region 11 includes a plurality of pixels so as to have a touch sensor function that senses an operator's touch operation (hereinafter also simply referred to as touch). The detection area 13 is divided into drive areas 14-1, 14-2, 14-3, and 14-4 including a plurality of pixels. In FIG. 1, the sensing area 13 is schematically shown as an area surrounded by a dotted line. In FIG. 1, the drive regions 14-1, 14-2, 14-3 and 14-4 are schematically shown as regions surrounded by broken lines.

  In the liquid crystal display element 10, first common wirings 15-1, 15-2, 15-3, and 15-4 extending in the horizontal direction (horizontal direction) in the figure are provided in the display region 11. The first common wirings 15-1, 15-2, 15-3, and 15-4 are common wirings for connecting the plurality of common electrodes 12 arranged in a matrix in the display region 11 in the left-right direction. .

  In the drive region 14-1, two common electrodes 12 arranged on the left and right in the upper side of the figure are electrically connected by the first common wiring 15-1, and similarly, in the drive region 14-3, the upper side of the figure The two common electrodes 12 arranged on the left and right are electrically connected by the first common wiring 15-1. Therefore, the four common electrodes 12 arranged in the left-right direction of the drive region 14-1 and the drive region 14-3 are electrically connected by the first common wiring 15-1.

  At this time, the common electrode 15-1 is not electrically connected to the common electrode 12 in the sensing region 13 sandwiched from the left and right by the drive region 14-1 and the drive region 14-3.

  Similarly to the first common wiring 15-1, the four common electrodes 12 arranged in the left-right direction of the drive region 14-1 and the drive region 14-3 are electrically connected by the first common wire 15-2. The Further, the four common electrodes 12 arranged in the left-right direction of the drive region 14-2 and the drive region 14-4 are electrically connected by the first common wirings 15-3 and 15-4, respectively.

  At this time, the first common wirings 15-2, 15-3, and 15-4 are not electrically connected to the common electrode 12 in the sensing region 13.

  Further, in the display area 11, second common wirings 16-1, 16-2, 16-3, 16-4, 16-5, 16-6, 16-7 extending in the vertical direction (vertical direction) in the figure. , 16-8, 17-1, 17-2. The second common wires 16-1, 16-2, 16-3, 16-4, 16-5, 16-6, 16-7, 16-8, 17-1, 17-2 are provided in the display area 11. A plurality of common electrodes 12 arranged in a matrix form a common wiring for connecting in the vertical direction.

  For example, in the drive region 14-1, the two common electrodes 12 arranged in the vertical direction are electrically connected by the cross connection portion 20 by the second common wiring 16-1. Similarly, two common electrodes 12 arranged in the vertical direction are electrically connected by the second common wiring 16-2. Therefore, in the drive region 14-1, the four common electrodes 12 are electrically connected to each other by the first common wires 15-1 and 15-2 and the second common wires 16-1 and 16-2. There are two groups.

  Similar to the drive region 14-1, in the drive region 14-3, the four common electrodes 12 are formed by the first common wires 15-1 and 15-2 and the second common wires 16-3 and 16-4. They are electrically connected to each other to form one group. The four common electrodes 12 grouped in the drive region 14-1 and the four common electrodes 12 grouped in the drive region 14-3 are the first common wires 15-1, 15-. 2 are electrically connected to each other.

  In the drive region 14-2, the four common electrodes 12 are electrically connected to each other by the first common wires 15-3 and 15-4 and the second common wires 16-5 and 16-6. There are two groups.

  Similarly, in the drive region 14-4, the four common electrodes 12 are electrically connected to each other by the first common wires 15-3 and 15-4 and the second common wires 16-7 and 16-8. Constitute one group. The four common electrodes 12 grouped in the drive region 14-2 and the four common electrodes 12 grouped in the drive region 14-4 are first common wirings 15-3 and 15-. 4 are electrically connected to each other.

  On the other hand, in the sensing region 13, the common electrodes 12 contained therein are electrically connected and grouped by the second common wires 17-1 and 17-2. The second common wirings 17-1 and 17-2 are connected to the first common wirings 15-1, 15-2, 15-3, and 15-4 in the sensing region 13 at the first crossing 18. Electrical connection with the common wirings 15-1, 15-2, 15-3, and 15-4 is not made.

  Accordingly, in the driving region 14-1 and the driving region 14-3 that sandwich the sensing region 13 from the left-right direction in the figure, the common electrodes 12 included in them are electrically connected to each other, whereas in the sensing region 13 The common electrode 12 is not electrically connected to the common electrode 12 in the drive region 14-1 and the drive region 14-3. The first common wirings 15-1 and 15-2 that electrically connect the common electrode 12 in the drive region 14-1 and the common electrode 12 in the drive region 14-3 and the common electrode 12 in the sensing region 13 are electrically connected. The second common wirings 17-1 and 17-2 that are connected to each other constitute an intersecting portion 18 that is electrically insulated and is not connected to each other in the sensing region 13.

  Similarly, the common electrode 12 in the sensing region 13 is not electrically connected to the common electrode 12 in the drive region 14-2 and the drive region 14-4. Then, the first common wires 15-3 and 15-4 that electrically connect the common electrode 12 in the drive region 14-2 and the common electrode 12 in the drive region 14-4 and the common electrode 12 in the sensing region 13 are electrically connected. The second common wirings 17-1 and 17-2 that are connected to each other constitute an intersecting portion 18 that is electrically insulated and is not electrically connected to each other in the sensing region 13.

  The display area 11 of the liquid crystal display element 10 having the above configuration connects the common electrode 12 in the drive areas 14-1 to 14-4, the common electrode 12 in the sensing area 13, and the plurality of common electrodes 12 in the left-right direction. First common wires 15-1 to 15-4 for connecting the plurality of common electrodes 12 and second common wires 16-1 to 16-8, 17-1, and 17-2 for connecting the plurality of common electrodes 12 in the vertical direction. Thus, an electrode arrangement structure having the same function as that of the conventional touch panel 100 shown in FIG. 4 described above can be realized.

  That is, in the display region 11 of the liquid crystal display element 10, the common electrode 12 of the drive region 14-1 and the drive region 14-3 is connected to the first common wires 15-1 and 15-2 and the second common wire 16-1. The electrode structure similar to the first detection electrode 102 of the touch panel of FIG.

  Further, the common electrode 12 of the drive region 14-2 and the drive region 14-4 is also connected to the first common wires 15-3 and 15-4 and the second common wires 16-5 to 16-8. The same electrode structure as that of the first detection electrode 102 of the touch panel 4 is realized.

  Furthermore, in the display area 11 of the liquid crystal display element 10, the common electrode 12 in the sensing area 13 is connected to the second common wirings 17-1 and 17-2 in the same manner as the second detection electrode 104 of the touch panel in FIG. The electrode structure is realized.

  For example, the electrode structure realized by the common electrode 12 in the drive region 14-1 and the drive region 14-3 overlaps the electrode structure realized by the common electrode 12 in the sense region 13 in the sense region 13. The structure is electrically insulated from each other and is not connected. The same applies to the electrode structure realized by the common electrode 12 in the drive region 14-2 and the drive region 14-4.

  Therefore, as described above, in the display region 11 of the liquid crystal display element 10, an electrode arrangement structure having the same function as that of the conventional touch panel 100 shown in FIG. 4 is realized.

  Therefore, the liquid crystal display element 10 includes the arrangement structure of the common electrode 12 in the display region 11 as described above, the first common wires 15-1 to 15-4, and the second common wires 16-1 to 16-16. The connection structure using −8, 17-1, and 17-2 can have a touch sensor function for sensing a touch.

  FIG. 2 is a cross-sectional view schematically showing a part of the pixel structure of the sensing area of the display area of the liquid crystal display element according to the first embodiment of the present invention.

  The pixel 30 shown in FIG. 2 is the upper leftmost pixel of the sensing area 13 of the display area 11 of the liquid crystal display element 10 shown in FIG. That is, the pixel 30 is a pixel including the intersection 18 of the first common wiring 15-1 and the second common wiring 17-1 together with the common electrode 12, and FIG. 2 schematically shows the structure of the pixel 30. Show.

  2 shows the first substrate and the liquid crystal layer among the first substrate, the second substrate, and the liquid crystal layer constituting the liquid crystal display element 10, and faces the first substrate with the liquid crystal layer interposed therebetween. The illustration of the second substrate is omitted.

As shown in FIG. 2, the pixel 30 in the sensing area of the display area of the liquid crystal display element 10 has a TFT (Thin Film Transistor) 33 and a first common film on the surface of the first substrate 31 on the liquid crystal layer 32 side. The first layer 34 including the wiring 15-1, the second layer 35 including the common electrode 12 electrically connected to the second common wiring 17-1 and the second common wiring 17-1, and the TFT 33 A third layer 38 including a pixel electrode 36 and an interlayer insulating film 37 that are electrically connected to each other, and the pixel electrode 36 is opposed to the common electrode 12 of the second layer 35 with the interlayer insulating film 37 interposed therebetween. And the third layer 38 in this order.
In FIG. 1 described above, the common electrode 12 of the second layer 35 shown in FIG. 2 is schematically shown.

  As described above, the first layer 34 includes the TFT 33 and the first common wiring 15-1, and further includes the first insulating film 40 that covers and protects the TFT 33.

  The TFT 33 of the first layer 34 has a known structure, and forms a semiconductor layer 41, a gate insulating film 42 covering the semiconductor layer 41, and a part of a scanning signal line (not shown) on the semiconductor layer 41. A gate electrode 43 disposed through a gate insulating film 42, a source electrode 44 that forms part of a video signal line (not shown) and is electrically connected to the semiconductor layer 41, and is electrically connected to the semiconductor layer 41. The drain electrode 45 etc. to be connected are included.

The semiconductor layer 41 of the TFT 33 is formed using, for example, a-Si (amorphous-silicon) or microcrystalline silicon. Further, the gate insulating film 42 can be formed of, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN.

The first insulating film 40 of the first layer 34 can be formed of, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN.

  As described above, the second layer 35 includes the second common wiring 17-1 and the common electrode 12, and further includes the second insulating film 46 that covers the first layer 34. The second insulating film 46 preferably has a function as a planarizing film.

  The upper surface of the second insulating film 46 is flat. In the second layer 35, the common electrode 12 having a solid plate shape is provided on the second insulating film 46. The common electrode 12 can be formed, for example, by forming a film made of a transparent conductive material such as ITO using a sputtering method or the like and performing patterning using a photolithography method or the like.

  As described above, the third layer 38 disposed on the liquid crystal layer 32 side of the second insulating film 46 includes the pixel electrode 36 and the interlayer insulating film 37 that are electrically connected to the TFT 33. The pixel electrode 36 has a comb-like shape. The pixel electrode 36 is connected to the drain electrode 45 of the TFT 33 formed so as to penetrate the first insulating film 40 through a through hole that continuously penetrates the interlayer insulating film 37 and the second insulating film 46. Electrically connected.

  As described above, the interlayer insulating film 37 of the third layer 38 replaces a conventional inorganic interlayer insulating film made of SiN or the like, and is a coating type organic film using an organic material. The interlayer insulating film 37 is formed by coating using a radiation-sensitive resin composition according to a second embodiment of the present invention, which will be described in detail later, and is subjected to predetermined patterning using a photolithography method or the like. Formed.

  In the photolithography method, a process of forming a resist film by applying a resist composition such as a radiation-sensitive resin composition to the surface of a substrate to be processed or processed, and irradiating with light or an electron beam to form a predetermined film An exposure process for forming a resist pattern latent image by exposing the resist pattern, a heat treatment process if necessary, a development process for developing the resist pattern to form a desired fine pattern, and a substrate using the fine pattern as a mask Includes a step of performing processing such as etching.

  And the radiation sensitive resin composition of 2nd Embodiment of this invention mentioned later is the liquid crystal display element 10 of 1st Embodiment, In order to implement | achieve the dielectric constant and refractive index which the interlayer insulation film 37 desires, The composition has been optimized. That is, the radiation-sensitive resin composition of the second embodiment of the present invention contains a component for increasing the dielectric constant so that the interlayer insulating film 37 can be controlled to increase the dielectric constant.

  For example, the radiation-sensitive resin composition according to the second embodiment of the present invention includes [C] titanium oxide as a [C] component in addition to the [A] polymer and [B] photosensitizer as described later. And a compound containing at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium and lead. In addition, as will be described later, the radiation-sensitive resin composition of the present embodiment includes a polymer having at least one of [D] urethane bond and amide bond as a [D] component, and a urethane bond and amide bond. At least one selected from the group consisting of (meth) acrylate compounds having at least one of them can be included.

  Moreover, the radiation sensitive resin composition of 2nd Embodiment of this invention can raise the refractive index of the interlayer insulation film 37 formed using the above-mentioned [C] component by using it. . For example, in the liquid crystal display element 10 of the first embodiment, the refractive index of the interlayer insulating film 37 can be controlled within a range of 1.55 to 1.85, for example.

  And the radiation sensitive resin composition of 2nd Embodiment of this invention is excellent in patterning property, and also shows the outstanding adhesiveness and high hardening performance, and also [C] ] Component and [D] component can be used together, and optimal composition design is possible.

  As a result, the liquid crystal display element 10 is configured such that the dielectric constant and the like of the interlayer insulating film 37 are adjusted and can be easily replaced with a conventional inorganic interlayer insulating film made of SiN.

  Although the film thickness of the interlayer insulating film 37 is not particularly limited, it is preferable that the interlayer insulating film 37 has a thickness suitable for ensuring insulation between the common electrode 12 and the pixel electrode 36 and realizing a desired capacitance. . The film thickness of the interlayer insulating film 37 is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

  Further, the interlayer insulating film 37 is required to have excellent visible light transmittance as a constituent element constituting the pixel 30 of the liquid crystal display element 10. The interlayer insulating film 37 formed from the radiation sensitive resin composition of the second embodiment of the present invention has excellent transparency. As a result, the interlayer insulating film 37 can have a light transmittance of a wavelength of 400 nm of 85% or more, and can be 90% or more by selecting a component composition.

  Furthermore, the interlayer insulating film 37 has excellent adhesion as will be apparent from Examples described later.

  In the pixel 30 in the sensing region of the display region of the liquid crystal display element 10 having the above structure, the first common wiring 15-1 and the second common wiring 17-1 intersect with each other through the first insulating film 40. It has the structure to do. That is, in the pixel 30, the first common wiring 15-1 and the second common wiring 17-1 intersect with each other via the first insulating film 40, and the first common wiring 15-1 and the second common wiring 17-1 intersect. The intersection 18 has a structure that is electrically insulated from the common wiring 17-1.

  FIG. 3 is a cross-sectional view schematically showing a part of the pixel structure in the drive region of the display region of the liquid crystal display element according to the first embodiment of the present invention.

  The pixel 50 shown in FIG. 3 is a pixel at the upper right end of the drive region 14-1 of the display region 11 of the liquid crystal display element 10 shown in FIG. That is, the pixel 50 is a pixel having a structure in which the second common wiring 16-2 and the first common wiring 15-1 electrically connected to the common electrode 12 are electrically connected by the cross-connecting portion 20. FIG. 3 schematically shows the structure of the pixel 50.

  FIG. 3 shows the first substrate and the liquid crystal layer among the first substrate, the second substrate, and the liquid crystal layer constituting the liquid crystal display element 10, and faces the first substrate with the liquid crystal layer interposed therebetween. The illustration of the second substrate is omitted.

  As shown in FIG. 3, the pixel 50 in the sensing area of the display area of the liquid crystal display element 10 is electrically connected at the cross-connecting portion 20 where the second common wiring 16-2 and the first common wiring 15-1 intersect. 2 has the same structure as that of the pixel 30 in FIG. Therefore, the same components as those of the pixel 30 in FIG. 2 are denoted by the same reference numerals, and redundant description is omitted.

As shown in FIG. 3, the pixel 50 in the drive region of the display region of the liquid crystal display element 10 includes a TFT 33 and a first common wiring 15-1 on the surface of the first substrate 31 on the liquid crystal layer 32 side. A second layer 39 including the common electrode 12 electrically connected to the second common wiring 16-2 and the second common wiring 16-2, and a pixel electrode 36 electrically connected to the TFT 33. And a third layer 38 including the interlayer insulating film 37, in which the pixel electrode 36 has a structure facing the common electrode 12 with the interlayer insulating film 37 interposed therebetween, in this order. Composed.
In FIG. 1 described above, the common electrode 12 of the second layer 39 shown in FIG. 3 is schematically shown.

  As described above, the first layer 34 includes the TFT 33 and the first common wiring 15-1, and further includes the first insulating film 40 that covers and protects the TFT 33. Accordingly, the pixel 50 in the driving area shares the first common wiring 15-1 with the pixel 30 in the sensing area shown in FIG.

  The TFT 33 of the first layer 34 has a known structure as described above, and forms a semiconductor layer 41, a gate insulating film 42 covering the semiconductor layer 41, and a part of a scanning signal line (not shown). A gate electrode 43 disposed on the layer 41 via a gate insulating film 42; a source electrode 44 that forms part of a video signal line (not shown) and is electrically connected to the semiconductor layer 41; and the semiconductor layer 41 The drain electrode 45 and the like are electrically connected to each other.

  As described above, the second layer 39 includes the second common wiring 16-2 and the common electrode 12, and further includes the second insulating film 46 covering the first layer 34.

  The upper surface of the second insulating film 46 is flat, and the common electrode 12 having a solid plate shape is provided thereon.

  As described above, the third layer 38 provided on the liquid crystal layer 32 side of the second insulating film 46 includes the pixel electrode 36 and the interlayer insulating film 37 that are electrically connected to the TFT 33.

  In the pixel 50 in the drive region of the display region of the liquid crystal display element 10 having the above structure, the first common wiring 15-1 and the second common wiring 16-2 are cross-connected through the first insulating film 40. It has a structure that intersects at the portion 20. At this time, as described above, the first common wiring 15-1 is shared with the pixels 30 in the sensing region shown in FIG. 2, and the second common wiring 16-2 is a pixel. 30 is different from the second common wiring 17-1. In the cross connection portion 20 of the pixel 50, the first common wiring 15-1 and the second common wiring 16-2 are mutually connected by the connection portion 19 that forms part of the second common wiring 16-2. A structure for electrical connection is formed.

  Therefore, in the pixel 50 in the drive region, the common electrode 12 is electrically connected to the first common wiring 15-1 via the second common wiring 16-2. By having such a structure, the liquid crystal display element 10 detects that the common electrode 12 of the pixel 50 in the drive region is connected to the first common wiring 15-1, as will be described later, when the touch sensor function is used. It can be used as an electrode.

  As described above, the sensing region pixel 30 shown in FIG. 2 and the driving region pixel 50 shown in FIG. 3 have the TFT 33 on the first substrate 31, and the TFT 33 is electrically connected to the TFT 33. A comb-like pixel electrode 36 to be connected has a structure in which it is superimposed on the solid plate-like common electrode 12 with an interlayer insulating film 37 interposed therebetween. That is, the liquid crystal display element 10 according to the first embodiment of the present invention including the pixel 30 of FIG. 2 and the pixel 50 of FIG. 3 constitutes an FFS mode liquid crystal display element.

  When the image display function is used, the liquid crystal display element 10 uses the TFTs 33 of the pixels 30 and 50 as switching elements, while applying a common voltage to the common electrode 12 of the pixels 30 using the second common wiring 17-1. In addition, a common voltage is supplied to the common electrode 12 of the pixel 50 using the second common wiring 16-2. A desired image can be displayed by driving the liquid crystal layer 32 disposed between the first substrate 31 and the second substrate.

  Furthermore, the liquid crystal display element 10 can use the common electrode 12 of the pixels 30 and 50 as a detection electrode when using the touch sensor function. That is, the common electrode 12 of the pixel 30 that is electrically connected to the second common wiring 17-1 is used as a detection electrode, and is connected to the first common wiring 15-1 via the second common wiring 16-2. The common electrode 12 of the pixel 50 that is electrically connected can be used as the detection electrode.

  The liquid crystal display element 10 uses the common electrode 12 of the pixel 50 in the driving region and the common electrode 12 of the pixel 30 in the sensing region, and a driving signal is applied to the first common wiring 15-1 so that the second common A sensing signal is configured to be detected from the wiring 17-1. As a result, the liquid crystal display element 10 changes the capacitance between the first common wiring 15-1 and the second common wiring 17-1, particularly the first common wiring 15-at the intersection 18 of the pixel 30. It is possible to sense a touch in the display area by sensing a change in capacitance between the first and second common wirings 17-1.

  That is, in the liquid crystal display element 10, when the touch sensor function is used, a change in capacitance between the first common wiring 15-1 and the second common wiring 17-1 is sensed using the pixels 30 in the sensing area. In addition, touch detection in the display area can be performed.

  As described above, the liquid crystal display element 10 according to the first embodiment of the present invention can have both an image display function and a touch sensor function for sensing a touch.

  At this time, the liquid crystal display element 10 of the first embodiment of the present invention is configured by disposing an interlayer insulating film 37 that is an organic film between the pixel electrode 36 and the common electrode 12, and the interlayer insulating film The effect of 37 can also reduce the problem of bone appearance.

Embodiment 2. FIG.
<Radiation sensitive resin composition>
The liquid crystal display element according to the first embodiment of the present invention described above has an interlayer insulating film between the opposing pixel electrode and the common electrode for insulating them from each other. The interlayer insulating film can be manufactured using the radiation-sensitive resin composition of the second embodiment of the present invention. The radiation sensitive resin composition of this embodiment is a resin composition provided with radiation sensitivity. And the radiation sensitive resin composition of this embodiment can have either positive radiation sensitivity or negative radiation sensitivity.

  The radiation-sensitive resin composition of the present embodiment includes a [A] polymer that is the [A] component, a [B] photosensitive agent that is the [B] component, and a [C] titanium oxide that is the [C] component. And a compound containing at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium and lead (hereinafter sometimes simply referred to as [C] compound) as an essential component. .

  And when the radiation sensitive resin composition of this embodiment is a positive type radiation sensitive resin composition, [B] a photosensitive agent is a photo-acid generator or contains a photo-acid generator. Is preferred. Moreover, when the radiation sensitive resin composition of this embodiment is a negative radiation sensitive resin composition, [B] a photosensitizer is a radical photopolymerization initiator or contains radical photopolymerization initiator It is preferable to do.

  Furthermore, the radiation-sensitive resin composition of the present embodiment includes a [D] urethane bond and an amide bond, which are [D] components, in order to control the dielectric properties of the insulating film of the embodiment of the present invention obtained. It contains at least one selected from the group consisting of a polymer having at least one and a (meth) acrylate compound having at least one of a urethane bond and an amide bond (hereinafter sometimes simply referred to as [D] compound). Is preferred.

  Moreover, unless the radiation sensitive resin composition of this embodiment impairs the effect of this invention, you may contain another arbitrary component.

  Hereinafter, each component contained in the radiation sensitive resin composition of this embodiment is demonstrated in detail.

[[A] polymer]
In the radiation sensitive resin composition of the second embodiment of the present invention, the [A] polymer as the component [A] is a base of an interlayer insulating film formed using the radiation sensitive resin composition of the present embodiment. It is a component that becomes a material.

  And it is preferable that the [A] polymer is alkali-soluble resin so that the radiation sensitive resin composition of this embodiment may be provided with the desired patterning property. In that case, the [A] polymer is not particularly limited as long as it is a polymer having alkali developability. However, the polymer corresponding to the above-mentioned [D] compound is excluded.

  As a preferable [A] polymer, the polymer containing the structural unit which has a carboxyl group can be mentioned.

  The [A] polymer is an unsaturated double layer so that the interlayer insulating film of the liquid crystal display element of the first embodiment of the present invention can be formed as a cured film using the radiation-sensitive resin composition of the present embodiment. Those containing structural units having a bond or a polymerizable group such as an epoxy group are more desirable. Therefore, as the [A] polymer, a polymer containing a structural unit having a carboxyl group and further containing a structural unit having a polymerizable group is more preferable.

  In this case, in the [A] polymer, the preferred structural unit having a polymerizable group is at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. (Hereafter, it may be called a specific structural unit.) [A] When the polymer contains the specific structural unit, a cured film having excellent surface curability and deep part curability, that is, an interlayer insulating film of the liquid crystal display element of the first embodiment of the present invention is formed. be able to.

  The structural unit having the (meth) acryloyloxy group is, for example, a method of reacting an epoxy group in a copolymer with (meth) acrylic acid, a (meth) acryl having an epoxy group in a carboxyl group in the copolymer By a method of reacting an acid ester, a method of reacting a (meth) acrylic acid ester having an isocyanate group with a hydroxyl group in the copolymer, a method of reacting (meth) acrylic acid at an acid anhydride site in the copolymer, etc. Can be formed. Among these, a method of reacting a carboxyl group in the copolymer with a (meth) acrylic ester having an epoxy group is preferable.

  The [A] polymer containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group is at least selected from the group consisting of (A1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. One kind (hereinafter also referred to as “(A1) compound”) and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”) can be copolymerized and synthesized. . In this case, the [A] polymer includes a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound. It becomes a copolymer containing.

  [A] The polymer is obtained by, for example, copolymerizing a compound (A1) that provides a carboxyl group-containing structural unit and a compound (A2) that provides an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. When the radiation-sensitive resin composition of the present embodiment is a positive type, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) is further included. In addition, it can be a copolymer. Further, in the production of the [A] polymer, the compound (A4) (derived from the compounds (A1), (A2) and (A3)) together with the compound (A1), the compound (A2) and the compound (A3). An unsaturated compound that gives a structural unit other than the structural unit) may be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) Compound]
Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.

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

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

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

  Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like. It is done.

  Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.

  These (A1) compounds may be used alone or in combination of two or more.

  The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-25 mass% are more preferable. (A1) By making the usage-amount of a compound into 5 mass%-30 mass%, while the solubility with respect to the alkaline aqueous solution of [A] alkali-soluble resin is optimized, the interlayer insulation film excellent in radiation sensitivity is obtained.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [ 5.2.1.0 ^2.6 ] decyl (meth) acrylate and the like.

  Specific examples of the copolymer of the compound (A1) and the compound (A2) include, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922. And JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, JP-A-4-352101, and the like. Can do.

  In the present embodiment, as the [A] polymer, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-09-325494, It is also possible to use a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain as disclosed in Kaihei 11-140144, JP-A-2008-181095, and the like. it can.

  [A] The polymer has a polystyrene-reduced weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1000 to 100,000, preferably 3000 to 50000. The ratio of the weight average molecular weight of the binder polymer in this embodiment to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably 1. 0-3.0.

  [A] polymer of this embodiment can be manufactured by a well-known method, For example, in Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, international publication 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the disclosed method.

[[B] Photosensitizer]
[B] Photosensitive agent contained in the radiation-sensitive resin composition of the second embodiment of the present invention is a compound capable of initiating polymerization by generating radicals in response to radiation (that is, [B-1] photoradical. Polymerization initiator) or a compound that generates an acid in response to radiation (that is, [B-2] photoacid generator). The radiation sensitive resin composition of this embodiment can have radiation sensitivity by containing [B] a photosensitizer, for example, has positive radiation sensitivity or negative radiation sensitivity. Can do.

[B-1] Photoradical polymerization initiator Examples of the [B-1] photoradical polymerization initiator of the radiation-sensitive resin composition of the present embodiment include O-acyloxime compounds, acetophenone compounds, and biimidazole compounds. . These compounds may be used alone or in combination of two or more.

  Examples of O-acyloxime compounds include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

  Among the above-mentioned acetophenone compounds, α-aminoketone compounds are preferable, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 are more preferred.

  As these (B-1) photoradical polymerization initiators, it is possible to use the photopolymerization initiators described in JP2013-164471A, JP2012-212114A, and JP2010-85929A. it can.

  [B-1] The content of the radical photopolymerization initiator is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the component [A]. . By setting the content of the radical photopolymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition of the present embodiment has high solvent resistance, high hardness and high even at a low exposure amount. An interlayer insulating film having adhesiveness can be formed.

[B-2] Photoacid Generator Next, as described above, the [B-2] photoacid generator, which is the [B] photosensitizer of the radiation-sensitive resin composition of the present embodiment, is irradiated by radiation. It is a compound that generates acid. 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. The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation.

  [B-2] Examples of the photoacid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinone diazide compounds.

As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (1) is preferable. In the formula, R ^a is an alkyl group, a cycloalkyl group, or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent.

In the above formula (1), R ^a is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

  Specific examples of the oxime sulfonate compound include [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5H-octylsulfonyloxyimino-5H-thiophene-2- Ylidene)-(2-methylphenyl) acetonitrile], [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H- Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like.

  In addition, the photoacid generators described in JP2011-227106A and JP2012-150494A can be used.

  Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and sulfonimide compound.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethyl). Phenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diph Cycloalkenyl maleimide, N- hydroxynaphthalimide - trifluoromethanesulfonic acid ester and the like.

  As other photoacid generators, the photoacid generators described in JP2011-215503A and WO2011 / 087011A1 can be used.

  The content of the [B-2] photoacid generator in the radiation-sensitive resin composition of the present embodiment is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the [A] component, and 1 mass. Part-5 mass parts is more preferable. The radiation sensitivity of the radiation sensitive resin composition of the present embodiment can be optimized, exhibits good patternability, and is suitable for forming an interlayer insulating film.

  Moreover, a quinonediazide compound can also be mentioned as a [B-2] photo-acid generator of the radiation sensitive resin composition of this embodiment. This quinonediazide compound can be particularly preferably used as the [B-2] photoacid generator.

  A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 85 mol%, more preferably 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  These quinonediazide compounds include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho. A condensate of quinonediazide-5-sulfonic acid chloride (2.0 mol) is preferably used.

  These quinonediazide compounds can be used alone or in combination of two or more.

  Moreover, it can also be used in combination with the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonic acid ester compound and carboxylic acid ester compound described above.

  As content of the quinonediazide compound in the radiation sensitive resin composition of this embodiment, Preferably it is 5 mass parts-100 mass parts with respect to 100 mass parts of [A] component, More preferably, it is 10 mass parts-50 masses. Part. By setting the content of the quinonediazide compound in the above range, the difference in solubility between the irradiated portion 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, the solvent resistance of the interlayer insulation film obtained using this radiation sensitive resin composition can also be made favorable.

[[C] Compound containing titanium oxide and metal element]
[C] component of the radiation sensitive resin composition of 2nd Embodiment of this invention is at least 1 sort (s) of metal element chosen from the group which consists of titanium oxide and barium, strontium, calcium, magnesium, zirconium, and lead. (Hereinafter, simply referred to as [C] compound). In the radiation-sensitive resin composition of the present embodiment, the component [C] is a component that enables control to improve the dielectric constant and refractive index of the interlayer insulating film of the liquid crystal display element of the first embodiment of the present invention. .

  Examples of the above-mentioned [C] compound include barium titanate, strontium titanate, calcium titanate, magnesium titanate, zirconium titanate and lead titanate.

  These [C] compounds may be used individually by 1 type, or can also be used in combination of 2 or more type.

  [C] The shape of the compound is not particularly limited, and may be spherical or amorphous, and may be hollow particles, porous particles, core-shell type particles, or the like.

  Moreover, the particle diameter of a [C] compound can be calculated | required with the dynamic light-scattering method, and it is preferable that it is the range of 0.01 micrometer-0.1 micrometer. When the particle size of the compound [C] is in the above range, the desired patterning performance can be achieved in the radiation-sensitive resin composition of the present embodiment. Further, if the particle size of the [C] compound is less than 0.01 μm, the particles are likely to aggregate and storage stability may be lowered. If it exceeds 0.1 μm, the haze of the interlayer insulating film that is a cured film is high. There is a risk.

  In the [C] compound, the c / a axis ratio, which is the ratio of the c-axis length to the a-axis length of the crystal lattice, is preferably 1.0025 to 1.010. When the c / a axial ratio is in the range of 1.0025 to 1.010, both the particle diameter in the above range and excellent dielectric constant characteristics (high relative dielectric constant) can be realized.

And as a more preferable [C] compound of the radiation sensitive resin composition of this embodiment, a barium titanate and a strontium titanate can be mentioned from a viewpoint of high dielectric constant, As a particularly preferable [C] compound May include barium titanate (BaTiO ₃ ).

  When a particularly preferable barium titanate is selected as the [C] compound of the radiation-sensitive resin composition of the present embodiment, as described above, the shape thereof is not particularly limited, and may be spherical or amorphous. It may be hollow particles, porous particles, core / shell type particles, or the like.

  Further, the particle diameter of barium titanate particularly preferable as the [C] compound can be determined by the dynamic light scattering method as described above, and is preferably in the range of 0.01 μm to 0.1 μm. When the particle size of the compound [C] is in the above range, the desired patterning performance can be achieved in the radiation-sensitive resin composition of the present embodiment. In addition, if the particle size of the barium titanate [C] compound is less than 0.01 μm, the particles are likely to aggregate and storage stability may be reduced. The haze of the film may be increased.

  And in barium titanate especially preferable as a [C] compound, it is desirable that c / a axial ratio is 1.0025-1.010. When the c / a axial ratio is in the range of 1.0025 to 1.010, both the particle diameter in the above range and excellent dielectric constant characteristics (high relative dielectric constant) can be realized.

  [C] The compound is desirably dispersed in a dispersion medium together with a dispersant and used as a particle dispersion in the radiation-sensitive resin composition of the present embodiment. Thus, by containing a dispersing agent, in the radiation sensitive resin composition of this embodiment, a [C] compound can be disperse | distributed uniformly and applicability | paintability can be improved and the adhesiveness of the interlayer insulation film obtained is improved. The dielectric constant and the refractive index can be increased uniformly without bias.

  Examples of the dispersant include nonionic dispersants, cationic dispersants, anionic dispersants, and the like, but nonionic dispersants are preferable from the viewpoint of improving positive radiation sensitivity and patterning properties. Examples of such nonionic dispersants include polyoxyethylene alkyl phosphate esters, amide amine salts of high molecular weight polycarboxylic acids, ethylenediamine PO-EO condensates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, alkyl glucosides, polyoxyethylenes. Mention may be made of oxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or fatty acid alkanolamides.

  The dispersion medium is not particularly limited as long as the [C] compound can be uniformly dispersed. A dispersion medium can function a dispersing agent effectively, and can disperse | distribute a [C] compound uniformly.

  Examples of the dispersion medium include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethylene Ethers such as glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether; esters such as propylene glycol monomethyl ether acetate and methyl-3-methoxypropionate; dimethylformamide, N, N-dimethyl Amides such as acetoacetamide and N-methylpyrrolidone; acetone, methyl ethyl ketone Methyl isobutyl ketone and cyclohexanone; benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene. Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, methanol, isopropyl alcohol, and propylene glycol monomethyl ether are preferable. Methyl ethyl ketone, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, methyl-3- Methoxypropionate is more preferred. The dispersion medium can be used alone or in combination of two or more.

  Content of the [C] compound in the dispersion liquid mentioned above becomes like this. Preferably they are 5 mass%-50 mass%, More preferably, they are 10 mass%-40 mass%.

  In the radiation sensitive resin composition of 2nd Embodiment of this invention, it is although it does not specifically limit as a compounding quantity of a [C] compound, It is 0.1 mass part-1500 mass with respect to 100 mass parts of [A] component. Part is preferable, and 1 part by mass to 1000 parts by mass is more preferable. When the compounding amount of the [C] compound is less than 0.1 parts by mass, the effect of improving the dielectric constant of the obtained interlayer insulating film cannot be obtained sufficiently. On the other hand, when the compounding amount of the [C] compound exceeds 1500 parts by mass, the applicability of the radiation-sensitive resin composition of the present embodiment is lowered, and the desired patterning performance may not be obtained. Further, the haze of the obtained interlayer insulating film may be increased.

[[D] Polymer having at least one of urethane bond and amide bond and (meth) acrylate compound]
The radiation-sensitive resin composition of the second embodiment of the present invention contains [A] a polymer, [B] a photosensitizer and a [C] compound as essential components, and [D] a urethane bond and an amide bond. At least one selected from the group consisting of a polymer having at least one of them and a (meth) acrylate compound having at least one of a urethane bond and an amide bond (hereinafter sometimes simply referred to as [D] compound. ) Can be included. In addition, the polymer which has at least one of the urethane bond and amide bond which are [D] compounds is polymers other than the above-mentioned [A] polymer.

  In the radiation sensitive resin composition of the present embodiment, the [D] compound is a component for improving the relative dielectric constant of the interlayer insulating film of the liquid crystal display element of the first embodiment of the present invention. By containing the [D] compound, the relative dielectric constant of the obtained interlayer insulating film can be improved. As a result, in the radiation-sensitive resin composition of the present embodiment, it is possible to adjust components in the direction of decreasing the content of the [C] compound, and patterning performance and insulating properties can be further improved.

  Since the compound [D] is used as a constituent component in the interlayer insulating film of the liquid crystal display element of the first embodiment of the present invention, which is formed as a cured film, the compound [D] Those having light or thermal crosslinking sites such as saturated double bonds are more desirable.

  As the (meth) acrylate compound having a urethane bond, commercially available urethane (meth) acrylate can be used.

  For example, commercially available products include AH-600 (phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer), AT-600 (phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer), UA-306H (pentaerythritol) manufactured by Kyoeisha Chemical Co., Ltd. Triacrylate hexamethylene diisocyanate urethane prepolymer), UA-306T (pentaerythritol triacrylate toluene diisocyanate urethane prepolymer), UA-306I (pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer), and UA-510H (dipentaerythritol penta). Acrylate hexamethylene diisocyanate urethane prepolymer ); Shin-Nakamura Chemical Co., Ltd. U-4HA, U-6HA, U-6LPA, U-53H, A-9300, A-9300CL1, and UA-122P, Daicel-Cytec Ebecryl (registered trademark) 284, Ebecryl 285, Ebecryl294 / 25HD, Ebecryl4820, Ebecryl4858, Ebecryl8402, Ebecryl8405, Ebecryl9270, Ebecryl8311, Ebecryl8701, Ebecryl230, Ebecryl244, Ebecryll245, Ebecryl264, Ebecryl265, Ebecryl270, Ebecryl280 / 15IB, Ebecryl1259, Ebecryl5129, Ebecryl8210, Ebecryl830 , Ebecryl8307, Ebecryl8411, Ebecryl8804, Ebecryl8807, Ebecryl9227EA, Ebecryl9250, KRM (registered trademark) 8200, KRM7735, KRM8296, KRM8452, Ebecryl204, Ebecryl205, Ebecryl210, Ebecryl215, Ebecryl220, and Ebecryl6202; Nippon Synthetic Chemical Industry Co., Ltd. UV-1700B, UV -6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-7650B, etc .; Daiichi Kogyo Seiyaku R-1214, R-1220 , R-1301, R-1304, R-1306X, -1308, R-1602, and R-1150D; and Negami Industrial Co., Ltd. UN-333, UN-1255, UN-2600, UN-2700, UN-5500, UN-6060PTM, UN-6060P, UN-6200, UN-6300, UN-6301, UN-7600, UN-7700, UN-9000PEP, UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN- 905, UN-952, UN-9600, UN-906, and the like.

  These (meth) acrylate compounds can be used alone or in combination of two or more.

  In addition, the polyurethane resin which is an example of a polymer having a urethane bond is not particularly limited, but for example, a polyurethane resin obtained by reacting an isocyanate group with a polyol to extend a chain is preferable. Examples of the polyol include polyester polyol, polyether polyol, and acrylic polyol. Examples of commercially available polyurethane resins include the Juliano series (Arakawa Chemical Co., Ltd.), the Olester series (Mitsui Chemicals Co., Ltd.), the Arotane series (Nippon Shokubai Co., Ltd.), and the like.

  These polyurethane resin products may be used alone or in combination of two or more.

  Examples of the (meth) acrylate compound having an amide bond include (meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- Butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-di Chill (meth) acrylamide.

  These (meth) acrylate compounds can be used alone or in combination of two or more.

  Examples of the polymer having an amide bond include a polymer formed by using the above-mentioned (meth) acrylate compound having an amide bond as a constituent component or an additive in a raw material composition.

  As for content of the [D] compound in the radiation sensitive resin composition of this embodiment, 1 mass%-20 mass% are preferable with respect to the whole radiation sensitive resin composition. Moreover, when the radiation sensitive resin composition of this embodiment contains an organic solvent, content of the [D] compound in a radiation sensitive resin composition is 5 mass% with respect to the sum total of the component except an organic solvent. It is preferable to be within a range of ˜50% by mass or less, and it is more preferable to be within a range of 10% by mass to 40% by mass. When the compound [D] is contained in the above range, an excellent patterning performance can be realized in the radiation-sensitive resin composition, and an interlayer insulating film having an improved relative dielectric constant can be obtained.

<Other optional components>
The radiation-sensitive resin composition according to the second embodiment of the present invention is within a range that does not impair the effects of the present invention, and other components such as an acid diffusion controller, a surfactant, an adhesion assistant, and inorganic oxide particles as necessary. These optional components may be contained. Other optional components may be used alone or in combination of two or more.

  Surfactant is a component which improves the film-forming property of the radiation sensitive resin composition of this embodiment. The radiation sensitive resin composition of this embodiment can improve the surface smoothness of the coating film by containing a surfactant, and as a result, interlayer insulation formed from the radiation sensitive resin composition of this embodiment. The film thickness uniformity can be further improved.

  The adhesion assistant is a component that improves the adhesion between a film formation target such as a substrate and the interlayer insulating film. The adhesion assistant is particularly useful for improving the adhesion between the inorganic substrate and the cured film. As the adhesion assistant, a functional silane coupling agent is preferable.

<Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition according to the second embodiment of the present invention includes, in addition to the above-described [A] polymer, [B] photosensitizer, and [C] compound, as needed, the [D] compound, It is prepared by mixing a surfactant, which is a multi-optional component. At this time, an organic solvent can be used to prepare a radiation-sensitive resin composition in a dispersion state. An organic solvent can be used individually or in mixture of 2 or more types.

  Examples of the function of the organic solvent include adjusting the viscosity and the like of the radiation-sensitive resin composition of the present embodiment, and improving operability and the like in addition to improving applicability to a substrate and the like. It is done. As a viscosity of the radiation sensitive resin composition implement | achieved by containing organic solvents etc., 0.1 mPa * s-50000 mPa * s (25 degreeC) are preferable, for example, More preferably, 0.5 mPa * s-10000 mPa * are preferable. s (25 ° C.).

  Examples of the organic solvent that can be used in the radiation-sensitive resin composition of the present embodiment include those that dissolve or disperse other components and that do not react with other components.

  For example, alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones And other esters. As the solvent, the solvents described in JP2011-232632 can be used.

  The content of the organic solvent used in the radiation sensitive resin composition of the present embodiment can be appropriately determined in consideration of viscosity and the like.

  As a dispersion method when preparing a radiation-sensitive resin composition in a dispersion state, the particle speed is usually 5 m / s to 15 m / s using a paint shaker, SC mill, annular mill, pin mill, etc. It is good to carry out by the method of continuing until the fall of a diameter is no longer observed. This duration is usually several hours. In this dispersion, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is preferably 0.05 mm to 0.5 mm, more preferably 0.08 mm to 0.5 mm, and still more preferably 0.08 mm to 0.2 mm.

  Next, the manufacturing method of the interlayer insulation film of 3rd Embodiment of this invention performed using the radiation sensitive resin composition of 2nd Embodiment of this invention is demonstrated.

Embodiment 3 FIG.
<Method for producing interlayer insulating film>
In the method for manufacturing an interlayer insulating film of the third embodiment of the present invention, an interlayer insulating film is formed as a patterned cured film on a substrate using the radiation-sensitive resin composition of the second embodiment of the present invention. Thus, it is preferable to include at least the following steps [1] to [3] in the following order.

  In that case, as the substrate, for example, the first substrate 31 of the liquid crystal display element 10 of the first embodiment of the present invention such as FIG. 2 described above can be used. That is, using the first substrate 31 in which the first layer 34 and the second layer 35 are arranged in this order on the surface on the liquid crystal layer 32 side, desired patterning is performed on the second layer 35. An interlayer insulating film can be formed.

  Hereinafter, the manufacturing method of the interlayer insulation film of this embodiment is demonstrated.

[1] Coating film forming step of forming a coating film of the radiation sensitive resin composition of the second embodiment of the present invention [2] Exposure step of irradiating at least part of the coating film formed in step [1] [3] Development step of developing the coating film irradiated with radiation in step [2]

  Below, each process of [1]-[3] is demonstrated.

[1] Coating film forming process In the process [1] (coating film forming process), the radiation-sensitive resin composition of the second embodiment of the present invention is applied onto a substrate. Next, the coated surface is preferably heated (prebaked), and when the solvent is contained in the coating film, the solvent is removed to form the coating film.

  As described above, the substrate may be the first substrate 31 in which the first layer 34 and the second layer 35 in FIG. And about the structure of the 1st board | substrate 31, it is preferable to use the transparent substrate excellent in visible-light transmittance. Examples of the transparent substrate that can be used include a glass substrate and a resin substrate as described above. Specific examples of the resin substrate include polyethylene terephthalate film, polybutylene terephthalate film, polyethylene film, polypropylene film, polyethersulfone film, polycarbonate film, polyacryl film, polyvinyl chloride film, polyimide film, and cyclic olefin ring-opening polymer. The film etc. which consist of a film and its hydrogenated substance can be mentioned.

  It does not specifically limit as a coating method of the radiation sensitive resin composition to a board | substrate. For example, an appropriate 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 ink jet method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C. for 1 to 10 minutes.

[2] Exposure Step In step [2] (exposure step), at least a part of the coating film on the substrate formed in step [1] is irradiated with radiation (hereinafter also referred to as exposure). In this case, when a part of the coating film is exposed, it is usually exposed through a photomask having a predetermined pattern suitable for forming an interlayer insulating film of the liquid crystal display element. Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure dose in step [2] is preferably 100 J / m ^{2 to} 10,000 J / m ² , more preferably 100 J / m ^{2 to} 10,000 J / m ² , as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). is ^{500J / m 2 ~6000J / m 2} .

[3] Development Step In step [3] (development step), the exposed coating film obtained in step [2] is developed, so that unnecessary portions (the coating film of the radiation sensitive resin composition is positive). In the case of (1), the radiation-irradiated portion (in the case of the negative type, the non-irradiated portion) is removed, and an interlayer insulating film subjected to predetermined patterning is formed.

  As the developer used in the development step, it is preferable to use an alkali developer which is an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline developer. The concentration of alkali in the alkali developer is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Subsequent to such development processing, for example, after washing with running water for 30 seconds to 90 seconds, an interlayer insulating film having a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen. it can.

  In addition, after the development, the interlayer insulating film may be further cured by further exposure as necessary. Moreover, you may heat-process at 80 to 280 degreeC instead of exposure after image development, or together with exposure.

  Thus, the interlayer insulating film on the substrate formed by the steps [1] to [3] has high transparency and a high refractive index. The interlayer insulating film formed from the radiation-sensitive resin composition of the present embodiment has a high refractive index of 1.50 or more, further 1.55 or more, although it varies depending on the blending ratio of each component. Yes.

  The thickness of the interlayer insulating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

  As described above, the interlayer insulating film produced using the radiation-sensitive resin composition according to the second embodiment of the present invention has a patterning property, transparency, It has adhesion and insulation, and has a desired range of dielectric constant controlled by the components of the radiation-sensitive resin composition.

  Therefore, it can be suitably used as an interlayer insulating film of the liquid crystal display element of the first embodiment of the present invention.

  Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.

<[A] Synthesis of polymer>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl 3-methoxypropionate. Subsequently, (a-1) 20.0 parts by mass of methacrylic acid, (a-2) 3-methacryloyloxymethyl-3-ethyloxetane 20 parts by mass, (a-3) 30.0 parts by mass of styrene, (a- 4) After charging 30 parts by mass of tricyclo [5.2.1.0 ^2,6 ] dec-8-yl methacrylate and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1) as a copolymer (solid content concentration = 29.1% by mass). Mw = 6800, Mw / Mn = 1.8).

<Preparation of [C] compound dispersion>
In a plastic bottle or glass bottle, 25 parts by mass of (C-1) (BaTiO ₃ (powder)) as [C] compound, 5 parts by weight of (I-1) as [I] dispersant, (G -2) Add 70 parts by mass of (1-methoxy-2-propanol), add 0.1 μm zirconia beads for 3.5 times the charged weight, seal, lightly stir, solvent, particle components and organic Blended with ingredients. This was set in a paint shaker, dispersed for 3 hours, and zirconia beads were removed with a mesh filter to obtain a [C] compound dispersion (C-1).

<Preparation of radiation-sensitive resin composition>
[Example 1]
[A] In the polymer solution containing (A-1) as a polymer, [B] Radiation sensitivity as a photosensitizer with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer. 10 parts by weight of a polymerization initiator (B-1), 100 parts by weight (solid content) of a [C] compound dispersion (C-1), 100 parts by weight of (D-1) as a compound [D] which is a high dielectric organic component Part, [E] 5 parts by mass of (E-1) as an adhesion assistant, and [F] 0.10 parts by mass of (F-1) surfactant are mixed, and the solid content concentration is 30% by mass. [G] After being dissolved and dispersed in (G-1) and (G-2) as organic solvents, the mixture was filtered through a membrane filter having a pore size of 0.2 μm, and the radiation-sensitive resin composition ( S-1) was prepared.

  Details of each component used in the examples are shown below.

<[B] Radiation sensitive polymerization initiator>
B-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Ciba Specialty Chemicals, Irgacure ( Registered trademark) OXE02)

<[C] Compound>
C-1: BaTiO ₃ (powder) (Toda Kogyo Co., Ltd., T-BTO-020)

<[D] Compound>
D-1: 6-functional urethane acrylate (Negami Kogyo Co., Ltd., Art Resin UN-906)

<[E] Adhesion aid>
E-1: γ-Glycidoxypropyltrimethoxysilane (Chisso Corporation, S-510)

<[F] Surfactant>
F-1: Silicone surfactant (Toray Dow Corning Silicone, SH28PA)

<[G] Organic solvent>
G-1: Ethyl 3-methoxypropionate G-2: 1-methoxy-2-propanol

<[I] Dispersant>
I-1: Phosphate ester salt (Big Chemie Japan, BYK-102)

<Physical evaluation of radiation sensitive resin composition and cured film>
A cured film was formed from the radiation-sensitive resin composition prepared as described above, and the physical properties were evaluated.

[Example 2]
(Preparation of patterning evaluation board)
Using the radiation-sensitive resin composition (S-1) prepared in Example 1 and applying it on a Si (silicon) wafer with a spin coater so that the film thickness after curing is 0.5 μm, Pre-baking was performed at 90 ° C. for 100 seconds, and the organic solvent was evaporated to form a coating film. Next, using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), 100 mJ of UV light was irradiated through a pattern mask capable of forming a predetermined pattern. Thereafter, using a tetramethylammonium hydroxide aqueous solution (developer) having a concentration of 2.38% by mass, development processing was performed at 25 ° C. for 100 seconds by a liquid piling method. After the development processing, each coating film was washed with running ultrapure water for 1 minute and dried, and then a patterned cured film was formed on the Si wafer.

[Example 3]
(Evaluation of patterning properties)
A 20 μm × 20 μm hole pattern penetrating through the cured film produced as described above was observed with an optical microscope, and the degree of residue was evaluated. The patterning property was evaluated as A when the residue could not be confirmed, B when the residue could be confirmed slightly, C when the residue could be clearly confirmed, and D when the residue could be confirmed in large quantities.

  As a result of the evaluation, the patterning property of the cured film formed in Example 2 was A evaluation.

[Example 4]
(Evaluation of transmittance)
The radiation sensitive resin composition prepared in Example 1 was applied to a glass substrate (“Corning 7059” (manufactured by Corning)) with a spin coater, and then pre-baked at 90 ° C. for 2 minutes on a hot plate. Formed. Next, exposure was performed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and development was performed using a 0.5 mass% tetramethylammonium hydroxide aqueous solution. After drying, for the glass substrate on which this cured film is formed, the light transmittance in the wavelength range of 400 nm to 800 nm is measured using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.), The minimum value of the light transmittance in the wavelength range of 400 nm to 800 nm (also referred to as the minimum light transmittance) was evaluated. Then, the light transmittance at a wavelength of 400 nm was used as a reference for evaluation, 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. As a result of the evaluation, the transmittance of the cured film was 96%.

  The cured film obtained using the radiation-sensitive resin composition prepared in Example 1 had a light transmittance of 90% or more at a wavelength of 400 nm, and the light transmittance characteristics were particularly good.

[Example 5]
(Evaluation of adhesion)
After applying the radiation sensitive resin composition prepared in Example 1 on an ITO substrate, which is a glass substrate with an ITO film, using a spin coater, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form each coating film. . Next, exposure is performed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and development is performed using an aqueous tetramethylammonium hydroxide solution having a concentration of 0.4% by mass, and curing is performed on the ITO substrate. A film was formed.

  For the ITO substrate for evaluation on which the above-mentioned cured film was prepared, the number of grids remaining in 100 grids was obtained by performing “8.5.3 Adhesive grid tape method of JIS K-5400-1990”. And the adhesion of the cured film was evaluated.

  As a result of the evaluation, the number of remaining grids was 100, and the cured film obtained using the radiation-sensitive resin composition prepared in Example 1 had good adhesion.

[Example 6]
(Production of electrical property evaluation board)
The radiation-sensitive resin composition (S-1) prepared in Example 1 was applied on an ITO substrate, which is a glass substrate with an ITO film, with a spin coater so as to have a film thickness of 1 μm. Prebaking was performed at 100 ° C. for 100 seconds, and the organic solvent was evaporated to form a coating film. Next, as an electrode extraction site for measuring electrical characteristics, a part of the end of the substrate coated with the radiation-sensitive resin composition was wiped with acetone to expose the underlying ITO. Subsequently, 100 mJ of UV light was irradiated with a UV exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ) to form an insulating film on the ITO substrate.

[Example 7]
(Measurement of dielectric constant)
An Al (aluminum) electrode for measuring electrostatic capacity is vacuum-deposited on the cured film of the electrical property evaluation substrate prepared by the method described in [Production of electrical property evaluation substrate] of Example 6 described above. (JEOL VACUUM EVAPOATOR JEE-420). Next, a lead wire for electrode connection is soldered to the ITO portion of the substrate that has been exposed in advance, and the lead wire and the Al electrode produced by a vacuum deposition apparatus are respectively connected to an LCR meter (HEWRET PACKARD 4284A PRECISION LCR METER). The capacitance C of the insulating film was measured under the conditions of an applied voltage of 100 mV and a frequency of 1000 Hz, connected to the plus terminal and the minus terminal. The value of the dielectric constant ε was obtained by substituting the measured value of the capacitance C, the area S (m ² ) of the Al electrode, and the thickness d (m) of the cured film into the following equation. The value of the dielectric constant ε was 5.0.

[Example 8]
(Leakage current measurement method)
Leakage current measurement using the substrate whose dielectric constant was measured in [Measurement of dielectric constant] in Example 7 described above, and connecting electrodes (lead wire and Al electrode) to an electrometer (KEITHLEY 6517A ELECTROMETER / HIGH REISTANCE METER) The leakage current was measured by applying a voltage between the electrodes sandwiching the cured film so as to be connected to the terminal of the box (KEITHLEY 8002A HIGH RESISTANCE TEST FIXTURE) and to have an electric field strength of 50 V / μm. Since the value of the leak current varies immediately after the start of measurement, the value 1 minute after the start of measurement was evaluated as the leak current value. As a result of the evaluation, the leak current value was 5.2 × 10 ⁻⁷ A (ampere), which was a very small value. The cured film obtained using the radiation-sensitive resin composition prepared in Example 1 had good insulation.

  As described above, the cured film formed using the radiation-sensitive resin composition of Example 1 has excellent patternability, transmittance characteristics, and adhesion, and further has a high dielectric constant and excellent properties. It has been found that it has insulating properties and can be suitably used as an interlayer insulating film of a liquid crystal display element.

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

  The liquid crystal display element of the present invention incorporates a touch sensor function, has high reliability, and can be easily manufactured at low cost. Therefore, the liquid crystal display element of the present invention having a built-in touch sensor function is suitable not only for portable information devices such as smartphones but also for display elements of larger stationary electrical devices.

DESCRIPTION OF SYMBOLS 10 Liquid crystal display element 11 Display area 12 Common electrode 13 Sensing area 14-1, 14-2, 14-3, 14-4 Drive area 15-1, 15-2, 15-3, 15-4 1st common wiring 16-1, 16-2, 16-3, 16-4, 16-5, 16-6, 16-7, 16-8, 17-1, 17-2 Second common wiring 18 Crossing portion 19 Connection portion 20 Cross connection part 30, 50 Pixel 31 First substrate 32 Liquid crystal layer 33 TFT
34 first layer 35, 39 second layer 36 pixel electrode 37, 105 interlayer insulating film 38 third layer 40 first insulating film 41 semiconductor layer 42 gate insulating film 43 gate electrode 44 source electrode 45 drain electrode 46 second Two insulating films 100 Touch panel 101 Substrate 102 First detection electrode 104 Second detection electrode

Claims (14)

A liquid crystal layer is sandwiched between a first substrate and a second substrate which are arranged to face each other, and a plurality of pixels arranged in a matrix form in a display region, and an image display function and a touch sensor function for sensing touch In a liquid crystal display device comprising:
At least some of the plurality of pixels are
On the liquid crystal layer side of the first substrate,
A first layer including a TFT and a first common wiring;
A second layer including a second common wiring and a common electrode connected to the second common wiring;
A pixel electrode connected to the TFT and an interlayer insulating film, the pixel electrode having a third layer having a structure facing the common electrode via the interlayer insulating film in this order;
The interlayer insulating film is an organic film;
When the image display function is used, a common voltage is supplied to the common electrode of the pixel using the second common wiring,
The liquid crystal is configured to sense the touch by sensing a change in capacitance between the first common wiring and the second common wiring when the touch sensor function is used. Display element. The interlayer insulating film is
[A] polymer,
[B] a photosensitive agent, and [C] a radiation-sensitive resin composition comprising a compound containing titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium, and lead. The liquid crystal display element according to claim 1, wherein the liquid crystal display element is formed using a liquid crystal.   [A] The liquid crystal display element according to claim 2, wherein the polymer is a polymer containing a structural unit having a carboxyl group.   [B] The liquid crystal display element according to claim 2, wherein the photosensitive agent contains at least one selected from a photo radical polymerization initiator and a photo acid generator.   The compound [C] has a particle diameter in the range of 0.01 μm to 0.1 μm and a c / a axial ratio of 1.0025 to 1.010. A liquid crystal display element according to item.   The liquid crystal display element according to any one of claims 2 to 5, wherein the [C] compound is barium titanate.   The radiation sensitive resin composition further comprises [D] a polymer having at least one of a urethane bond and an amide bond and a (meth) acrylate compound having at least one of a urethane bond and an amide bond. The liquid crystal display element according to claim 2, comprising at least one selected from the group.   The liquid crystal display element according to claim 1, wherein the liquid crystal display element is an FFS mode liquid crystal display element. [A] polymer,
[B] a photosensitive agent, and [C] a radiation-sensitive resin composition comprising a compound containing titanium oxide and at least one metal element selected from the group consisting of barium, strontium, calcium, magnesium, zirconium, and lead. Because
A radiation-sensitive resin composition, which is used for forming an interlayer insulating film included in the liquid crystal display element according to claim 1.   [A] The radiation-sensitive resin composition according to claim 9, wherein the polymer is a polymer containing a structural unit having a carboxyl group.   [B] The radiation-sensitive resin composition according to claim 9 or 10, wherein the photosensitive agent contains at least one selected from a photo radical polymerization initiator and a photo acid generator.   The compound [C] has a particle diameter in the range of 0.01 μm to 0.1 μm, and a c / a axial ratio of 1.0025 to 1.010. The radiation-sensitive resin composition according to item.   The radiation-sensitive resin composition according to any one of claims 9 to 12, wherein the [C] compound is barium titanate.   [D] includes at least one selected from the group consisting of a polymer having at least one of a urethane bond and an amide bond, and a (meth) acrylate compound having at least one of a urethane bond and an amide bond. The radiation-sensitive resin composition according to any one of claims 9 to 13, wherein

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