JP6536067B2 - METHOD FOR MANUFACTURING LIQUID CRYSTAL DISPLAY DEVICE, RADIATION-SENSITIVE RESIN COMPOSITION, AND LIQUID CRYSTAL DISPLAY DEVICE - Google Patents

Description

  The present invention relates to a method of manufacturing a liquid crystal display device, a radiation sensitive resin composition, and a liquid crystal display device.

  The liquid crystal display element has a structure in which liquid crystal is held between a pair of oppositely disposed substrates. Electrodes can be provided on these substrates, and an alignment film can be provided on the surface of each substrate for the purpose of controlling the alignment of the liquid crystal. Also, the pair of substrates is held, for example, by a pair of deflection plates. Then, when an electric field is applied between the substrates, the liquid crystal is driven to change the alignment, and light is partially transmitted or blocked. The liquid crystal display device displays an image using such characteristics. Such a liquid crystal display element has an advantage that it can be made thinner and lighter than the conventional CRT type display device.

  In liquid crystal display devices, various liquid crystal modes different in initial alignment state of liquid crystal and alignment change operation are known. For example, there are liquid crystal modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Planes Switching), FFS (Fringe Field Switching), VA (Vertical Alignment) and OCB (Optically Compensated Birefringence).

  The liquid crystal display element at the beginning of development was used as a display element of a calculator or a clock mainly for displaying characters and the like. After that, the development of the simple matrix system made the dot matrix display easy, and the application was expanded to the display elements of notebook computers. Subsequently, development of an active matrix system in which thin film transistors (TFTs) for switching are disposed in each pixel has made it possible to realize excellent image quality with excellent contrast ratio and response performance. Furthermore, the liquid crystal display device overcomes the problems such as high definition, colorization and widening of the viewing angle, and is used also as a monitor of a desktop computer. Recently, a wider viewing angle, faster response of liquid crystal, improved display quality, etc. are realized, and it is used as a display for large and thin television display elements and displays for portable electronic devices such as smartphones that require high density display. It has been used.

  Such liquid crystal display devices are increasingly required to have high image quality in recent years with the expansion of applications as described above. In particular, in displays for medical equipment and liquid crystal televisions, black display is regarded as very important, and a liquid crystal display element capable of uniform black display with low luminance and no display unevenness is strongly demanded. .

  As described above, the liquid crystal display element has a structure in which liquid crystal is held between a pair of oppositely disposed substrates, and the display area is constituted by a large number of pixels. In order to realize uniform black display and to realize high image quality, it is important to make the thickness (cell gap) of liquid crystal uniform in each pixel.

  In a liquid crystal display element, as a method of making the thickness of liquid crystal between substrates uniform, for example, a method of dispersing and arranging bead spacers which are spherical spacer members between a pair of substrates, and either of a pair of substrates There is known a method of forming spacers projecting in a columnar shape on one of the substrates. In particular, in a liquid crystal display device capable of realizing uniform black display and realizing high image quality, a method of forming columnar spacers on either one of a pair of substrates is mainly used (for example, Patent Document 1) See).

JP, 2010-152188, A

  In a liquid crystal display element, for example, a manufacturing method using a liquid crystal dropping method is effective to cope with the increase in size. In the liquid crystal dropping method, after dropping a liquid crystal on one of the prepared pair of substrates, the liquid crystal can be attached to the other substrate, and the liquid crystal can be interposed between the pair of substrates.

  And, in the liquid crystal display element, in the case where the above-described columnar spacer is provided, a structure is known in which a step is provided on the spacer. That is, by forming the spacer formed on the substrate from, for example, two types of spacers having different heights, the spacer can be provided with a level difference. The structure in which the step is provided on the spacer is particularly effective for the liquid crystal dropping method described above.

  When a step is provided on a spacer on a substrate in the manufacture of a liquid crystal display element, by sticking a pair of substrates together, the spacer includes one whose tip is not in contact with the opposing substrate surface . That is, in some of the plurality of spacers on the substrate, a gap is formed between the tip thereof and the surface of the counter substrate. In the liquid crystal display device provided with such a spacer, the alignment for substrate bonding by the liquid crystal dropping method becomes easy at the time of manufacture, and the margin in the substrate bonding process can be expanded.

  And in the liquid crystal display element of the structure which provided the level | step difference in the spacer, at the time of normal use, the spacer formed higher among the spacers functions so as to ensure the uniformity of the cell gap. That is, a spacer formed such that its tip is in contact with the opposing substrate surface improves the uniformity of the cell gap. On the other hand, when a pressure such as pressing is applied to the liquid crystal display element from the outside, the lower one of the spacers also functions as a support for the substrate. That is, the spacer provided so that the tip forms a gap between the opposing substrate also acts as a support for the substrate, and the fluctuation of the cell gap can be suppressed to improve the external pressure resistance.

  A spacer provided with such a step can be formed by patterning using a photosensitive spacer forming member. In that case, when exposing the spacer forming member, a plurality of types of spacers having different heights can be obtained by lowering the mask opening with a part of the mask for patterning or providing a light shielding film with an arbitrary transmittance. It is possible to form.

  However, when it is going to form the spacer provided with the level | step difference by the method as mentioned above, especially in the several spacer by which the height is formed lower, it is difficult to form them in uniform height . Further, the spacers formed at a lower height are likely to have variations in height on the substrate, and there is a concern that the yield at the time of bonding the substrates may be lowered in the manufacture of the liquid crystal display element.

  Also, in recent years, as described above, in the liquid crystal display element, high definition of pixels has been promoted. Therefore, when it is going to form a spacer on a substrate as a high-definition pattern, with the spacer in which the level difference was provided, the variation in height became large in the spacer formed lower height, and it had become a problem.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a method of manufacturing a liquid crystal display element in which the height variation of the spacer is small and the spacer is provided with a step.

  Another object of the present invention is to provide a radiation sensitive resin composition which is used in the manufacture of a liquid crystal display device in which the height variation of the spacer is small and the spacer is provided with a step.

  Another object of the present invention is to provide a liquid crystal display device in which the height variation of the spacers is small and the spacers have steps.

  Other objects and advantages of the present invention will become apparent from the following description.

According to a first aspect of the present invention, a plurality of spacers are provided on the second substrate of the first substrate and the second substrate disposed opposite to each other.
An insulating film is provided on the first substrate, and a spacer pedestal is provided on at least one of the portions of the insulating film facing the tip of the spacer,
It is a manufacturing method of a liquid crystal display element formed by sandwiching liquid crystal between the first substrate and the second substrate,
(1) a coating film forming step of forming a coating film of a radiation sensitive resin composition on the first substrate,
(2) an exposure step of irradiating the coating film with radiation using at least one selected from a halftone mask and a gray tone mask;
(3) a developing step of developing the coating film irradiated with the radiation, and (4) a heating step of heating the developed coating film, and having the spacer pedestal on the first substrate The present invention relates to a method of manufacturing a liquid crystal display device, including forming an insulating film at one time.

In the first aspect of the present invention, in the (2) exposure step, radiation is irradiated using at least one selected from the halftone mask and the gray tone mask to coat the coating film of the radiation sensitive resin composition, Providing at least two parts with different doses of radiation;
By the (3) developing step and the (4) heating step, one of the two parts of the (2) exposure step forms the insulating film and the spacer pedestal disposed thereon. It is preferable that the other one part forms the said insulating film.

In the first aspect of the present invention, the radiation sensitive resin composition is
It is preferable to contain [A] a polymer containing a structural unit having a carboxyl group, and [B] a radiation sensitive compound.

  In the first aspect of the present invention, the polymer containing a structural unit having a carboxyl group contained in the radiation sensitive resin composition preferably further has a crosslinkable group.

  1st aspect of this invention WHEREIN: The said crosslinkable group which the polymer which contains the structural unit which has a [A] carboxyl group which the said radiation sensitive resin composition has is an oxetanyl group, an oxynyl group, and (meth) acryloyl group. It is preferable that it is at least one selected from the group consisting of groups.

  In the first aspect of the present invention, the polymer containing a structural unit having the [A] carboxyl group contained in the radiation sensitive resin composition is a polymer further having a structural unit represented by the following formula (1) Is preferred.

(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and 1 to 1 carbon atom This represents any one of alkoxy groups of 6. n represents an integer of 1 to 6.)

  In the first aspect of the present invention, the [B] radiation-sensitive compound is preferably an acid generator, a polymerization initiator or a combination thereof.

According to a second aspect of the present invention, a plurality of spacers are provided on the second substrate of the first substrate and the second substrate disposed opposite to each other, and an insulating film is provided on the first substrate. And a liquid crystal display element formed by sandwiching a liquid crystal between the first substrate and the second substrate, having a spacer pedestal on at least one of the portions on the insulating film facing the tip of the spacer. A radiation-sensitive resin composition used to collectively form the insulating film and the spacer pedestal by irradiation of radiation using at least one selected from a halftone mask and a gray tone mask,
The present invention relates to a radiation-sensitive resin composition comprising: [A] a polymer containing a structural unit having a carboxyl group; and [B] a radiation-sensitive compound.

  In the second aspect of the present invention, the polymer containing a structural unit having a carboxyl group [A] preferably further has a crosslinkable group.

  In the second aspect of the present invention, the crosslinkable group contained in the polymer containing a structural unit having a [A] carboxyl group is at least one selected from the group consisting of oxetanyl group, oxynyl group and (meth) acryloyl group. It is preferably a species.

  In the second aspect of the present invention, the polymer containing a structural unit having a carboxyl group [A] is preferably a polymer further having a structural unit represented by the following formula (1).

(In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and 1 to 1 carbon atom This represents any one of alkoxy groups of 6. n represents an integer of 1 to 6.)

According to a third aspect of the present invention, there is provided a plurality of spacers on the second substrate of the first substrate and the second substrate disposed opposite to each other.
An insulating film is provided on the first substrate, and a spacer pedestal is provided on at least one of the portions of the insulating film facing the tip of the spacer,
A liquid crystal display element in which liquid crystal is held between the first substrate and the second substrate,
The present invention relates to a liquid crystal display element characterized in that the insulating film on the first substrate and the spacer pedestal on the insulating film are collectively formed by the following steps (1) to (4). .
(1) a coating film forming step of forming a coating film of a radiation sensitive resin composition on the first substrate (2) radiation is applied to the coating film using at least one selected from a halftone mask and a gray tone mask Exposure step for irradiation (3) Development step for developing the coating film irradiated with the radiation (4) Heating step for heating the developed coating layer

In the third aspect of the present invention, the radiation sensitive resin composition is
It is preferable to contain [A] a polymer containing a structural unit having a carboxyl group, and [B] a radiation sensitive compound.

  According to the first aspect of the present invention, there is provided a method of manufacturing a liquid crystal display element in which the height variation of the spacer is small and the spacer is provided with a step.

  According to a second aspect of the present invention, there is provided a radiation-sensitive resin composition used in the manufacture of a liquid crystal display element in which the height variation of the spacer is small and the spacer is provided with a step.

  According to the third aspect of the present invention, a liquid crystal display element is provided in which the height variation of the spacer is small and the spacer is provided with a step.

It is sectional drawing which demonstrates typically the structure of the liquid crystal display element of 1st Embodiment of this invention. It is sectional drawing which demonstrates the structure of the conventional liquid crystal display element typically. It is a typical block diagram which shows an example of a structure of the liquid crystal display element of 1st Embodiment of this invention. It is a typical circuit diagram explaining an example of a circuit configuration of a pixel of a liquid crystal display element of a 1st embodiment of the present invention. It is a top view which illustrates typically a pixel part of a liquid crystal display element which is an example of a 1st embodiment of the present invention. It is sectional drawing which shows typically the cross-section which followed the A-A 'line | wire of FIG.

  FIG. 1 is a cross-sectional view schematically illustrating the structure of the liquid crystal display element according to the first embodiment of the present invention.

  In FIG. 1, only the first substrate 2, the second substrate 3, the spacer 4, the insulating film 5 and the spacer pedestal 6 are shown so that the features of the liquid crystal display element 1 according to the first embodiment of the present invention become clear. Other components are omitted for the sake of convenience. The insulating film 5 also shows a contact hole 7 for electrically connecting an electrode or the like (not shown) disposed thereon and an electrode or the like (not shown) provided on the second substrate 3. ing.

  As shown in FIG. 1, the liquid crystal display element 1 according to the first embodiment of the present invention is a first substrate of the second substrate 3 out of the first substrate 2 and the second substrate 3 disposed opposite to each other. A plurality of spacers 4 are provided on the surface on the two side, and an insulating film 5 is provided on the surface on the second substrate 3 side of the first substrate 2. Furthermore, the liquid crystal display element 1 has a spacer pedestal 6 on at least one portion of the insulating film 5 facing the tip of the spacer 4. The liquid crystal display element 1 is configured by sandwiching liquid crystal (not shown) between the first substrate 2 and the second substrate 3.

  In the liquid crystal display element 1 according to the first embodiment of the present invention, the spacer pedestal 6 on the insulating film 5 of the first substrate 2 serves as a part of the insulating film 5 underlying the insulating film 5 together with the contact hole 7. And the insulating film 5 collectively. That is, in the liquid crystal display element 1, the insulating film 5 and the spacer pedestal 6 thereon have the contact holes 7 according to the method of manufacturing the liquid crystal display element of the second embodiment of the present invention described later. When the insulating film 5 is formed by patterning as described above, the insulating film 5 is integrally formed.

  In the liquid crystal display element 1 of the first embodiment of the present invention, the plurality of spacers 4 are formed on the second substrate 3 so as to have the same uniform height. Then, the tip of a part of the spacer 4 abuts against the spacer pedestal 6 formed on a part of the insulating film 5 so as to face the tip. On the other hand, in the remaining part of the spacers 4, that is, in the spacer 4 on which the spacer pedestal 6 is not provided on the opposing part of the insulating film 5 on the first substrate 2, the space between the opposing part There is a gap in the

  Therefore, in the liquid crystal display element 1 according to the first embodiment of the present invention, the plurality of spacers 4 are formed to have the same height on the second substrate 3, while the spacers 4 are provided with steps. There is. At this time, in the liquid crystal display element 1, since the plurality of spacers 4 are formed to have the same height, it is easy to reduce the height variation of the spacers. That is, in the liquid crystal display element 1 according to the first embodiment of the present invention, the height variation of the spacer can be reduced, and a step can be provided on the spacer.

  FIG. 2 is a cross-sectional view for schematically explaining the structure of a conventional liquid crystal display device.

  In FIG. 2, the first substrate 1002 and the second substrate of the conventional liquid crystal display element 1001 are the same as in FIG. 1 so that the difference in structure from the liquid crystal display element 1 of the first embodiment of the present invention becomes clear. Only the reference numeral 1003, the main spacer 1004, the sub spacer 1014 and the insulating film 1005 are shown, and other components are omitted for convenience. The insulating film 1005 also shows a contact hole 1007 for electrically connecting an electrode or the like (not shown) disposed thereon and an electrode or the like (not shown) provided on the second substrate 1003. ing.

  As shown in FIG. 2, the conventional liquid crystal display element 1001 is mainly formed on the surface of the second substrate 1003 on the side of the first substrate 1002 of the first substrate 1002 and the second substrate 1003 disposed opposite to each other. A spacer 1004 and a sub spacer 1014 are provided, and an insulating film 1005 is provided on the surface of the first substrate 1002 on the second substrate 1003 side. In the conventional liquid crystal display element 1001, the main spacer 1004 and the sub spacer 1014 are formed to have different heights on the second substrate 1003. The liquid crystal display element 1001 is configured by sandwiching liquid crystal (not shown) between the first substrate 1002 and the second substrate 1003.

  The main spacer 1004 of the conventional liquid crystal display element 1001 is formed higher than the sub spacer 1014 on the second substrate 1003. Then, the tip of the main spacer 1004 abuts on a part of the insulating film 5 opposed thereto. On the other hand, the sub spacer 1014 of the liquid crystal display element 1001 is formed to have a height lower than that of the main spacer 1004, and a gap is formed between the opposing portion of the insulating film 5.

  Therefore, in the conventional liquid crystal display element 1001, a step is provided between the main spacer 1004 and the sub spacer 1014. However, on the other hand, since the sub spacer 1014 is formed to have a height different from that of the main spacer 1004 so as to be lower, as described above, the height tends to vary. As a result, in the liquid crystal display element 1001, there is a concern that the yield of the substrate bonding step is lowered at the time of manufacturing.

  On the other hand, in the liquid crystal display element 1 according to the first embodiment of the present invention shown in FIG. 1, as described above, the height variation of the spacers 4 can be reduced and the spacers 4 can be provided with steps. As a result, unlike the conventional liquid crystal display element 1001 of FIG. 2, it is possible to suppress the decrease in the yield of the substrate bonding process at the time of its manufacture.

Hereinafter, an example of a more detailed structure of the liquid crystal display element 1 according to the first embodiment of the present invention will be described with reference to the drawings. Then, the manufacturing method of the liquid crystal display element of 2nd Embodiment of this invention and the radiation sensitive resin composition of 3rd Embodiment of this invention used therein are demonstrated.
In the present invention, the “radiation” irradiated at the time of exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

Embodiment 1
<Liquid crystal display element>
The liquid crystal display element of the first embodiment of the present invention can be used, for example, as a passive matrix liquid crystal display element or an active matrix liquid crystal display element. Active matrix liquid crystal display devices are used in displays (monitors) for portable electronic devices, displays for personal computers, displays for printing and design, displays for medical devices, liquid crystal televisions, and the like.

  FIG. 3 is a schematic diagram showing an example of the configuration of the liquid crystal display element according to the first embodiment of the present invention.

  FIG. 4 is a schematic circuit diagram for explaining an example of the circuit configuration of the pixel of the liquid crystal display element according to the first embodiment of the present invention.

  The liquid crystal display element 10 of the active matrix system shown in FIG. 3 is an example of the liquid crystal display element 1 of the first embodiment of the present invention shown in FIG. For example, as shown in FIG. 3, the liquid crystal display element 10 includes a liquid crystal display panel 31 for displaying an image, a first drive circuit 32, a second drive circuit 33, a control circuit 34, and a backlight 35. Be done.

  The liquid crystal display panel 31 has a plurality of scanning signal lines 36 and a plurality of video signal lines 37, and the video signal lines 37 are connected to the first drive circuit 32, respectively. It is connected to the second drive circuit 33.

  Although FIG. 3 shows five scanning signal lines 36 connected to the second drive circuit 33, this schematically shows a part of the plurality of scanning signal lines 36. In the actual liquid crystal display panel 31, a large number of scanning signal lines 36 are densely arranged. Similarly, although eight video signal lines 37 connected to the first drive circuit 32 are shown in FIG. 3, this schematically shows a part of the plurality of video signal lines 37. In the actual liquid crystal display panel 31, a large number of video signal lines 37 are densely arranged.

  Further, a display area 38 for displaying an image of the liquid crystal display panel 31 is configured as a set of a large number of pixels arranged in a matrix. An area occupied by one pixel in the display area 38 corresponds to, for example, an area surrounded by two adjacent scanning signal lines 36 and two adjacent video signal lines 37. At this time, the circuit configuration of one pixel is, for example, as shown in FIG. 4, and the TFT 43 functioning as an active element, the pixel electrode 42, the common electrode 41 (sometimes referred to as a counter electrode), and It has liquid crystal 40. Then, as shown in FIG. 4, the liquid crystal display panel 31 is provided with, for example, a commonization wiring 39 for making common electrodes 41 of a plurality of pixels in common.

  The liquid crystal display panel 31 is a TFT substrate (not shown in FIGS. 3 and 4) provided with the TFT 43, which is an example of the first substrate 2 of FIG. 1, and the second substrate 3 of FIG. As an example, it has a structure including an opposing substrate disposed opposite to the TFT substrate, and a liquid crystal 40 disposed between the TFT substrate and the opposing substrate. At this time, the TFT substrate and the counter substrate are bonded by an annular sealing material (not shown in FIGS. 3 and 4) provided outside the display region 38, and the liquid crystal 40 is a TFT substrate, It is sealed in the space surrounded by the opposing substrate and the sealing material. The liquid crystal display panel 31 of the liquid crystal display element 10 includes a TFT substrate, a liquid crystal 40, and a pair of polarizing plates (not shown in FIGS. 3 and 4) disposed facing each other with the opposing substrate interposed therebetween. In addition, the liquid crystal display element 10 is disposed on the back side opposite to the front side which is the viewer side, and includes a backlight 35 which emits light to the liquid crystal display panel 31 from the back side.

  The TFT substrate is a substrate in which the scanning signal line 36, the video signal line 37, the TFT 43 which is an active element, the pixel electrode 42 and the like are formed on an insulating substrate such as a glass substrate. Further, when the driving method of the liquid crystal display element 10 is a lateral electric field driving method such as IPS mode or FFS mode, the common electrode 41 and the commonizing wiring 39 of the liquid crystal display panel 31 are disposed on the TFT substrate. When the driving method of the liquid crystal display element 10 is vertical electric field driving method such as VA mode or TN mode, the common electrode 41 of the liquid crystal display panel 31 is disposed on the opposite substrate. In the case of the liquid crystal display element 1 of the vertical electric field drive system, the common electrode 41 of the liquid crystal display panel 31 is usually one large solid flat plate electrode shared by all pixels, and the common wiring 39 is Not provided.

  In the liquid crystal display element 10, the first drive circuit 32 is a drive circuit that generates a video signal (also referred to as a gradation voltage) to be applied to the pixel electrode 42 of each pixel through the video signal line 37. , A source driver, a data driver, and the like. The second drive circuit 33 is a drive circuit that generates a scan signal to be applied to the scan signal line 36, and is a drive circuit generally referred to as a gate driver, a scan driver, or the like.

  The control circuit 34 is a circuit that controls the operation of the first drive circuit 32, controls the operation of the second drive circuit 33, controls the brightness of the backlight 35, and the like. It is a control circuit called as etc.

  The backlight 35 is, for example, a light source such as a fluorescent lamp such as a cold cathode fluorescent lamp or a light emitting diode (LED), and light emitted from the backlight 35 is not shown. The light is converted to a planar light beam by a prism sheet or the like, and the liquid crystal display panel 31 is irradiated.

  The liquid crystal display element 10 as an example of the first embodiment of the present invention having the above configuration has a liquid crystal 40 sandwiched between the TFT substrate and the counter substrate, and a spacer having a columnar shape (FIG. 3 and FIG. 4). (Not shown)). That is, as in the liquid crystal display element 1 of FIG. 1, in the liquid crystal display element 10, the thickness of the liquid crystal 40 (also referred to as cell gap) in each pixel is uniform in the space where the liquid crystal 40 is sealed. There are provided a plurality of spacers for the conversion. In the liquid crystal display element 10, the plurality of spacers are provided on the counter substrate. Then, on the TFT substrate, a spacer pedestal (not shown in FIGS. 3 and 4) is provided in a portion of the insulating film facing the tip of the spacer.

  Hereinafter, the structure of the liquid crystal display element 10 as an example of the first embodiment of the present invention, in particular, the structure of the pixel of the liquid crystal display panel 31 provided with the spacer and the spacer pedestal will be described in more detail.

  FIG. 5 is a plan view schematically illustrating a pixel section of a liquid crystal display device which is an example of the first embodiment of the present invention.

  The liquid crystal display element 10 which is an example of 1st Embodiment of this invention is a liquid crystal display element of the FFS mode which is a horizontal electric field drive system.

  As shown in FIG. 5, in the liquid crystal display element 10, pixels are formed in each of the matrix-like regions surrounded by the scanning signal lines 36 and the video signal lines 37. In each pixel, a common electrode 41 formed of ITO (Indium Tin Oxide) in a flat and solid state is formed on the lower side, and an end portion of the common electrode 41 is shared for supplying a common potential to the common electrode 41 Wiring 39 is formed to overlap. A pixel electrode 42 having a slit is formed on the common electrode 41 with an insulating film described later interposed therebetween. When a video signal is supplied to the pixel electrode 42, an electric line of force is generated in the liquid crystal 40 (not shown in FIG. 5) between the common electrode 41 and the slit via a slit. The image can be formed by rotating in a plane parallel to the substrate surface to control the amount of light from the backlight not shown.

  As shown in FIG. 5, a TFT is formed on the scanning signal line 36. That is, the semiconductor layer 104 is formed on the scanning signal line 36 with the gate insulating film (not shown in FIG. 5) interposed therebetween. The drain electrode 105 is a branch of the video signal line 37. A source electrode 106 is formed to face the drain electrode 105, and the source electrode 106 extends to the pixel region and is electrically connected to the pixel electrode 42 through the contact hole 109.

  As shown in FIG. 5, a spacer pedestal 114 is formed on the scanning signal line 36. The spacer pedestals 114 are collectively formed integrally using the same forming material as the passivation film 107 (not shown in FIG. 5) provided so as to cover the scanning signal lines 36 on the TFT substrate 100. It is a thing. Further, an alignment film 113 (not shown in FIG. 5) is formed on the spacer pedestal 114. The tip of a columnar spacer 204 formed on the counter substrate is in contact with a portion corresponding to the spacer pedestal 114.

  FIG. 6 is a cross-sectional view schematically showing a cross-sectional structure taken along the line A-A 'of FIG.

  As shown in FIG. 6, a polarizing plate 120 is formed on the outside of the TFT substrate 100, and a polarizing plate 220 is formed on the outside of the counter substrate 200. The liquid crystal 40 is sandwiched between the TFT substrate 100 and the counter substrate 200. That is, in the liquid crystal display element 10 as an example of the first embodiment of the present invention, the liquid crystal 40 is sandwiched between the TFT substrate 100 and the counter substrate 200, and further sandwiched by the pair of polarizing plates 120 and 220 from the outside. Ru.

  As shown in FIG. 6, on the surface of the TFT substrate 100 on the liquid crystal 40 side, a common electrode 41 made of ITO, which is a transparent electrode, is formed. At the end of the common electrode 41, a common wiring 39 for supplying a common potential to the common electrode 41 is overlapped. The common electrode 41 is formed to be insulated from the scanning signal line 36.

  The scanning signal line 36 has a two-layer structure, the lower layer is formed of the same conductive layer 361 of ITO as the common electrode 41, and the upper layer is formed of the metal film 362 of the same metal as the common wiring 39. The metal film 362 forming the scanning signal line 36 can be formed of, for example, MoW or Al alloy.

  In the liquid crystal display element 10, the gate insulating film 103 is formed to cover the scanning signal line 36 and the common electrode 41, and the passivation film 107 as an example of the insulating film 5 in FIG. 1 is provided on the gate insulating film 103. ing. On the passivation film 107, a pixel electrode 42 is formed of ITO which is a transparent conductive material. On the other hand, on a part of the passivation film 107 on the scanning signal line 36, a spacer pedestal 114 formed collectively with the passivation film 107 is disposed. The spacer pedestal 114 integrally formed integrally with the passivation film 107 is an example of the spacer pedestal 6 of the insulating film 5 of FIG.

  And the passivation film 107 of the liquid crystal display element 10 is an insulating organic film formed using the radiation sensitive resin composition of 3rd Embodiment of this invention mentioned later. Then, the spacer pedestals 114 integrally formed integrally on the same also become an insulating organic member formed using the radiation sensitive resin composition of the third embodiment of the present invention.

  The spacer pedestal 114 formed on the passivation film 107 of the liquid crystal display element 10 can have a planar shape such as a square, a rectangle, a circle, an oval and an oval, etc. It is preferable to have a planar shape. At this time, as shown in FIG. 6, the upper end portion of the spacer pedestal 114 on the liquid crystal 40 side is formed to be higher than the upper end portion of the pixel electrode 42 on the liquid crystal 40 side.

  In FIG. 6, the passivation film 107 and the spacer pedestal 114 thereon are distinguished by broken lines, but the broken line in FIG. 6 is provided so that the spacer pedestal 114 is clear. For convenience, as described above, the spacer pedestal 114 and the passivation film 107 are integrally formed collectively using the same material.

  In the liquid crystal display element 10, the alignment film 113 is formed by applying an alignment agent for forming an alignment film on a TFT substrate having such a structure, curing the coating film, and performing an alignment process.

  Further, as shown in FIG. 6, a black matrix 201 and a color filter 202 are formed on the counter substrate 200. The black matrix 201 is arranged to cover the spacer pedestal 114 portion. Therefore, in this portion, even if the alignment control of the liquid crystal 40 is not sufficient, the light from the backlight is transmitted, and the display quality is not degraded.

  As shown in FIG. 6, an overcoat film 203 is formed to cover the color filter 202, and a columnar spacer 204 is formed on the overcoat film 203 so as to protrude toward the TFT substrate 100 side. . The spacer 204 is an example of the spacer 4 on the second substrate 4 of FIG.

  The spacer 204 can be formed on the counter substrate 200 by patterning using a radiation sensitive resin composition and using a photolithography method, for example. The spacer 204 can have, for example, a truncated cone shape whose flat end on the TFT substrate 100 side is flat. The spacer 204 can also be formed using the radiation sensitive resin composition of the third embodiment of the present invention for forming the passivation film 107 and the spacer pedestal 114. That is, like the passivation film 107, the spacer 204 can be formed using the radiation sensitive resin composition of the third embodiment of the present invention described later.

  Further, as shown in FIG. 6, the spacer 204 provided on the counter substrate 200 is disposed such that the tip thereof faces the spacer pedestal 114 disposed on the TFT substrate 100.

  In the counter substrate 200, the overcoat film 203 and the spacer 204 are covered, and an alignment film 113 similar to that of the TFT substrate is formed.

  When an alignment agent for forming the alignment film 113 is applied to the counter substrate 200, the alignment film 113 having a predetermined film thickness is formed on the overcoat film 203, but a columnar spacer 204 is provided to protrude. In some cases, the alignment film 113 is hardly formed on the tip of the light emitting diode by the leveling effect.

  In the liquid crystal display element 10 according to the first embodiment of the present invention having the above structure, the spacer 204 is provided on the counter substrate 200 sandwiching the liquid crystal 40 and the passivation film 107 of the other TFT substrate 100 is formed. A spacer pedestal 114 for receiving the spacer 204 is provided on the top. Therefore, in the liquid crystal display element 10, the thickness of the liquid crystal 40 can be formed uniformly.

  Then, in the liquid crystal display element 10 according to the first embodiment of the present invention, the spacer 204 is provided on the counter substrate 200 shown in FIG. 6 and the spacer 204 is received on the passivation film 107 of the TFT substrate 100. In addition to the structure for providing the spacer pedestal 114, it is also possible to include a structure (not shown) on the passivation film 107 where the spacer pedestal 114 is not provided in a portion facing the tip of the spacer 204. That is, for example, another spacer having the same height can be provided at a position different from the position where the spacer 204 is provided on the TFT substrate 100 of FIGS. 5 and 6. Here, the position at which another spacer of the same height is provided may be, for example, a different position on the scanning signal line 36 in FIG. 5 apart from the position at which the spacer 204 is provided. The spacer pedestal may not be provided in the portion of the passivation film 107 where the tip of the other spacer faces. In that case, a gap is formed between the tip of the other spacer and the portion of the passivation film 107 opposed thereto.

  Thus, in the liquid crystal display element 10 which is an example of the first embodiment of the present invention, the structure provided with the spacer pedestal 114 for receiving the spacer 204 on the TFT substrate 100 and the spacer pedestal 114 are not provided. By including the structure together, the structure of the liquid crystal display element 1 of FIG. 1 described above can be realized. That is, while the plurality of spacers 204 are formed on the TFT substrate 100 so as to have the same height, the spacers 204 can be provided with a step. And the liquid crystal display element 10 which is an example of 1st Embodiment of this invention can suppress the fall of the yield of a board | substrate bonding process at the time of the manufacture.

Embodiment 2
<Method of Manufacturing Liquid Crystal Display Device>
Next, a method of manufacturing the liquid crystal display element of the second embodiment of the present invention will be described.

  According to the method of manufacturing the liquid crystal display element of the second embodiment of the present invention, the liquid crystal display element of the first embodiment of the present invention described above can be manufactured. That is, in the method of manufacturing the liquid crystal display device according to the second embodiment of the present invention, the second substrate 3 of the first substrate 2 and the second substrate 3 disposed opposite to each other as shown in FIG. And the insulating film 5 on the first substrate 2, and at least one of the portions of the insulating film 5 facing the tip of the spacer 4 have the spacer pedestal 6, This is a method of manufacturing a liquid crystal display element in which liquid crystal (not shown) is held between the first substrate 2 and the second substrate 3.

  Here, as the first substrate, for example, the TFT substrate 100 of the liquid crystal display element 10 which is an example of the first embodiment of the present invention described with reference to FIG. 6 and the like can be used. That is, using the TFT substrate 100 in which the scanning signal line 36, the video signal line 37, the TFT 43 which is an active element, the pixel electrode 42 and the like are formed on an insulating substrate such as a glass substrate using a known method. Can. Thus, the first substrate can be prepared by known methods.

  Further, as the second substrate, for example, the opposite substrate 200 of the liquid crystal display element 10 which is an example of the first embodiment of the present invention described with reference to FIG. 6 and the like can be used. That is, on the insulating substrate such as a glass substrate, the black matrix 201 and the color filter 202 are formed by a known method, and the opposing substrate 200 having the overcoat film 203 covering the color filter 202 is used. be able to. A columnar spacer 204 can be formed on the overcoat film 203 of the counter substrate 200 so as to protrude toward the TFT substrate 100 according to a known method. Thus, the second substrate with the spacers can be prepared by known methods.

  From the above, with respect to the method of manufacturing the liquid crystal display element of the second embodiment of the present invention, referring to FIG. 1 as needed, the method of collectively forming the insulating film and the spacer pedestal on the first substrate, A method of manufacturing a substrate for a liquid crystal display device having an insulating film and a spacer pedestal will be described in detail.

(Method of manufacturing substrate having insulating film and spacer pedestal)
The method for forming the insulating film and the spacer pedestal included in the method for manufacturing a liquid crystal display element of the second embodiment of the present invention preferably includes the following steps [1] to [4] in this order.

  [1] A coating film forming step of forming a coating film of the radiation sensitive resin composition of the third embodiment of the present invention described later on the first substrate 2 (hereinafter referred to as “step [1]” is there.). Note that, as described above, the TFT substrate 100 of the liquid crystal display element 10 which is an example of the first embodiment of the present invention can be used as the first substrate 2 of this process.

[2] An exposure step of irradiating radiation to the coating film of the radiation sensitive resin composition formed in the step [1] using at least one selected from a halftone mask and a gray tone mask (hereinafter referred to as “step [2] There is a thing to say.).
[3] A development step of developing a coating film irradiated with radiation in step [2] (hereinafter sometimes referred to as "step [3]").
[4] A heating step of heating the coating film developed in step [3] (hereinafter sometimes referred to as "step [4]").

  According to the steps [1] to [4], it becomes possible to form a pattern of a predetermined shape made of resin on the first substrate 2, and insulation made of resin of a desired composition on the first substrate 2 The membrane 5 and the spacer pedestal 6 can be formed. That is, the insulating film 5 and the spacer pedestal 6 on the first substrate 2 shown in FIG. 1 can be integrally formed integrally.

  Hereinafter, the above-mentioned process [1]-process [4] are explained in more detail.

[Step [1]]
At this process, the coating film of the radiation sensitive resin composition of 3rd Embodiment of this invention mentioned later is formed on the 1st board | substrate 2. As shown in FIG. The radiation sensitive resin composition of the third embodiment of the present invention to be used will be described in detail later.

  After coating the radiation sensitive resin composition of the third embodiment of the present invention on one side of this substrate, prebaking is performed to evaporate a solvent such as an organic solvent to form a coating film.

  Examples of the material of the first substrate 2 include glass substrates such as soda lime glass and alkali-free glass, silicon substrates, or polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, aromatic polyamide, polyamide imide and polyimide Resin substrates, etc., and these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. It can also be done. And when using TFT substrate 100 of liquid crystal display element 10 which is an example of a 1st embodiment of the present invention as a 1st substrate as mentioned above, the above-mentioned glass substrate is used as a substrate which constitutes the TFT substrate 100 , Silicon substrates and resin substrates can be used.

  As a coating method of the radiation sensitive resin composition, for example, a spray method, a roll coating method, a spin coating method (sometimes referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method) A suitable method such as a bar coating method or an inkjet coating method can be adopted. Among these, the spin coating method or the slit coating method is preferable in that a film having a uniform thickness can be formed.

  Although the conditions of the above-mentioned prebaking differ depending on the kind of each component which constitutes the radiation sensitive resin composition, the compounding ratio, etc., it is preferable to carry out at a temperature of 70 ° C. to 120 ° C. Although it changes with heating apparatuses, it can be about 1 minute-about 10 minutes.

[Step [2]]
Next, in the present step, a group consisting of a halftone mask consisting of a semi-transmissive film, and a gray tone mask including a semi-transmissive region by slits, with respect to the coating on the first substrate 2 formed in step [1]. At least one selected from In this way, it is possible to preferably form an insulating film including portions having different film thicknesses, and it is possible to preferably form the insulating film 5 in which the spacer pedestal 6 is disposed and the contact hole 7 is formed.
The halftone mask or gray tone mask used in this step has a mask pattern corresponding to the shape of the insulating film 5 having the spacer pedestal 6 and the contact hole 7 shown in FIG.

  And when the radiation sensitive resin composition to be used has a positive type radiation sensitivity, the area | region in which the spacer base 6 was formed on the insulating film 5 shown in FIG. It becomes an area. Then, an area in which only the insulating film 5 is formed on the first substrate 2 and the spacer pedestal 6 is not formed is a half exposure area in which the irradiation amount of radiation is controlled. Further, the formation region of the contact hole 7 of the insulating film 5 is a full exposure region where radiation irradiation is performed without controlling the radiation dose.

  On the other hand, when the radiation sensitive resin composition to be used has negative radiation sensitivity, in the region shown in FIG. 1 where the spacer pedestal 6 is formed on the insulating film 5, the radiation dose is controlled. It becomes a full exposure area where radiation irradiation is performed. Then, an area in which only the insulating film 5 is formed on the first substrate 2 and the spacer pedestal 6 is not formed is a half exposure area in which the irradiation amount of radiation is controlled. In addition, the formation region of the contact hole 7 of the insulating film 5 is an unexposed region not irradiated with radiation.

  As the radiation used for the radiation irradiation, as described above, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The dose of radiation in the step [2] is preferably 100 J / m in the above-mentioned full exposure region as a value obtained by measuring the intensity of the radiation at a wavelength of 365 nm with an luminometer (OAI model 356, OAI Optical Associates Inc.) ^{2 ~10000J} / ^{m 2,} more preferably ^{500J / m 2 ~6000J / m 2} .
Then, in the above-described half-exposure region, the radiation amount is selected so as to have a smaller value that is more restricted than the radiation amount in these full-exposure regions, and radiation is applied.

[Step [3]]
Next, in the present step, the coating film after the irradiation of radiation obtained in the step [2] is developed to remove unnecessary portions, and a cured film having the spacer pedestal 6 and the contact hole 7 is provided. The patterns of the insulating film 5 are collectively formed. When the coating film of the radiation sensitive resin composition to be used is a negative type, the non-irradiated part of the radiation becomes an unnecessary part. Moreover, when the coating film of the radiation sensitive resin composition to be used is a positive type, the irradiated part of a radiation becomes an unnecessary part.

  As a developing solution used for the image development process of process [3], use of the alkaline developing solution which consists of aqueous solution of an alkali (basic compound) is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and quaternary ammonium salts such as tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to such an alkaline developer and used. The concentration of alkali in the alkali developer can be preferably 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 deposition method, a dipping method, a swing immersion 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. After such development processing, for example, after performing washing with flowing water for 30 seconds to 90 seconds, a pattern of insulating film 5 having a desired shape may be formed by, for example, air drying with compressed air or compressed nitrogen. it can.

[Step [4]]
Next, in the present step, the patterned coating on the first substrate 2 obtained in the step [3] is heated by a suitable heating device such as a hot plate or an oven to form a cured film, a spacer pedestal 6 An insulating film 5 having a predetermined shape and having contact holes 7 is formed. As heating temperature, 150 degreeC-350 degreeC is preferable. By setting the heating temperature to 150 ° C. or more, the coating can be sufficiently cured. Further, by setting the temperature to 350 ° C. or less, even if the first substrate 2 is configured using a resin substrate, its thermal deterioration can be prevented. From the above points, the heating temperature is more preferably 150 ° C. to 300 ° C. The curing time is, for example, preferably 5 minutes to 30 minutes on a hot plate, and 30 minutes to 180 minutes in an oven.

(Method of manufacturing liquid crystal display device)
According to the above, in the method of manufacturing the liquid crystal display device according to the second embodiment of the present invention, the second substrate 3 having the plurality of spacers 4 and the insulating film 5 in which the spacer pedestals 6 and the contact holes 7 are collectively formed. The first substrate 2 is prepared, and the liquid crystal display element is manufactured.

  First, on each of the first substrate 2 and the second substrate 3 described above, an alignment film (not shown in FIG. 1) for aligning liquid crystal is formed by a known method using a known liquid crystal alignment agent. Therefore form.

  Next, for example, a UV curable sealant (not shown in FIG. 1) is applied to a predetermined place on one of the first substrate 2 and the second substrate 3, and a known liquid crystal is applied. After the liquid crystal is further dropped to a predetermined number of places on the alignment film surface according to the dropping method, the other substrate is bonded so that the liquid crystal alignment film faces. Then, the liquid crystal between the substrates is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent, thereby manufacturing a liquid crystal display panel.

  It is desirable that the liquid crystal panel manufactured in this manner be further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment at the time of liquid crystal filling.

  From the above, the liquid crystal is disposed and sandwiched between the first substrate 2 and the second substrate 3 on which the alignment film is formed, and the liquid crystal display panel is manufactured. At this time, as a method of manufacturing a liquid crystal display panel, as another well-known method, the first substrate 2 and the second substrate 3 are opposed via a gap (cell gap) so that the alignment films are opposed. It is also possible to use a method of sealing the injection holes after placing, bonding the peripheral portions of the substrates together using a sealing agent, injecting and filling the liquid crystal into the substrate surface and the space partitioned by the sealing agent. .

  And the liquid crystal display element 1 of 1st Embodiment of this invention can be obtained by bonding a polarizing plate together to the outer surface of the obtained liquid crystal panel.

  The liquid crystal display element 1 according to the first embodiment of the present invention is, for example, as shown in FIG. 3, a known method for the first drive circuit 32, the second drive circuit 33, the control circuit 34, the backlight 35 and the like. Thus, the liquid crystal display element 10 which is an example of the first embodiment of the present invention can be configured.

  Next, the insulating film 5 (passivation of the liquid crystal display element 1 of the first embodiment of the present invention and the liquid crystal display element 10 as an example thereof, which is suitably used in the method of manufacturing the liquid crystal display element of the second embodiment of the present invention The radiation sensitive resin composition of the third embodiment of the present invention which can form the film 107) will be described.

Embodiment 3
Radiation-sensitive resin composition
The radiation sensitive resin composition of the third embodiment of the present invention can be suitably used for the formation of the insulating film in the liquid crystal display element of the first embodiment of the present invention. The radiation-sensitive resin composition of the third embodiment of the present invention is used to form a substrate having an insulating film and a spacer pedestal in the method of producing a liquid crystal display device of the second embodiment of the present invention described above. The insulating film can have a spacer pedestal integrally formed at a desired portion. That is, the coating film is formed on a predetermined substrate using the radiation sensitive resin composition of the third embodiment of the present invention, and after patterning using radiation sensitivity, the substrate is used as a cured film. An insulating film made of resin and a spacer pedestal can be integrally formed integrally on the top.

  At this time, the radiation sensitive resin composition of the present embodiment can select and provide either positive or negative radiation sensitivity.

  The radiation sensitive resin composition of the second embodiment of the present invention comprises a polymer containing a structural unit having a carboxyl group [A] and a radiation sensitive compound [B]. The radiation sensitive resin composition of the present embodiment is radiation sensitive. And the radiation sensitive resin composition of this embodiment can contain a [C] polymerizable unsaturated compound. Moreover, the radiation sensitive resin composition of this embodiment may contain other arbitrary components, unless the effect of this invention is impaired.

  Hereinafter, each component contained in the radiation sensitive resin composition of 2nd Embodiment of this invention is demonstrated.

(A polymer containing a structural unit having a [A] carboxyl group)
The polymer (hereinafter sometimes referred to simply as the [A] polymer) containing a structural unit having a carboxyl group, which is contained in the radiation sensitive resin composition of the third embodiment of the present invention,
(A1) Structural unit having a carboxyl group (hereinafter referred to as “structural unit (A1)”),
(A2) Structural units having crosslinkable groups (hereinafter referred to as "structural units (A2)") and (A3) structural units represented by the following formula (1) (hereinafter referred to as "structural units (A3)") Have. [A] The polymer may have a structural unit other than (A4) (A1) to (A3) (hereinafter referred to as "structural unit (A4)").

(In formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 3 to 12 carbon atoms The cycloalkyl group is any one of a cycloalkyl group, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group, and n is an integer of 1 to 6.)

The alkyl group having 1 to 6 carbon atoms of R ² in the above formula (1) may be linear, branched or cyclic. Specific examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and the like. Further, the cycloalkyl group having 3 to 12 carbon atoms R ² in the formula (1), for example, a cyclohexyl group or the like; as an alkoxy group having from 1 to 6 carbon atoms, such as methoxy group, an ethoxy radical, n And -propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy and the like can be mentioned.

The alkyl group having 1 to 6 carbon atoms of R ³ in the above formula (1) may be linear, branched or cyclic. Specific examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and the like. Further, the cycloalkyl group having 3 to 12 carbon atoms R ³ in the formula (1), for example, a cyclohexyl group or the like; as an alkoxy group having from 1 to 6 carbon atoms, such as methoxy group, an ethoxy radical, n And -propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy and the like can be mentioned.

The alkyl group having 1 to 6 carbon atoms of R ⁴ in the above formula (1) may be linear, branched or cyclic. Specific examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and the like. Further, the cycloalkyl group having 3 to 12 carbon atoms R ⁴ in the formula (1), for example, a cyclohexyl group or the like; as an alkoxy group having from 1 to 6 carbon atoms, such as methoxy group, an ethoxy radical, n And -propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy and the like can be mentioned.

  N in the above formula (1) is preferably an integer of 2 to 6, and particularly preferably 3 or 4.

  The structural unit (A2) is a structural unit having a crosslinkable group. The crosslinkable group is preferably at least one selected from the group consisting of an oxetanyl group, an oxynyl group and a (meth) acryloyl group. That is, the structural unit (A2) is a structural unit having at least one selected from the group consisting of an oxetanyl group, an oxynyl group and a (meth) acryloyl group.

The structural unit (A1) is a structural unit derived from at least one selected from the group consisting of (a1) unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as “compound (a1)”). Preferably there;
The structural unit (A2) is preferably a structural unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group (hereinafter referred to as “compound (a2)”);
The structural unit (A3) is preferably (a3) a structural unit derived from a compound represented by the following formula (a3) (hereinafter referred to as “compound (a3)”);
The structural unit (A4) is preferably a structural unit derived from a polymerizable unsaturated compound (hereinafter, referred to as “compound (a4)”) other than (a4) the above (a1) to (a3).

(R ¹ , R ² , R ³ , R ⁴ and n in the formula (a3) each have the same meaning as in the above formula (1).)

Examples of the compound (a1) include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and the like. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrate Hydrophthalic acid etc;
Examples of the dicarboxylic acids include maleic acid, fumaric acid, citraconic acid and the like;
Examples of the above-mentioned anhydrides of dicarboxylic acids include the above-mentioned anhydrides of dicarboxylic acids and the like.

Among them, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid or maleic anhydride are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained copolymer in a developer. preferable.
And a compound (a1) can be used individually or in mixture of 2 or more types.

  The compound (a2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an oxiranyl group and a polymerizable unsaturated compound having an oxetanyl group.

As the polymerizable unsaturated compound having an oxiranyl group, for example, (meth) acrylic acid oxiranyl (cyclo) alkyl ester, α-alkyl acrylic acid oxiranyl (cyclo) alkyl ester, glycidyl ether compound having a polymerizable unsaturated bond, etc .;
Examples of the polymerizable unsaturated compound having an oxetanyl group include, for example, (meth) acrylic acid esters having an oxetanyl group.

As specific examples of the above compound (a2),
As (meth) acrylic acid oxiranyl (cyclo) alkyl ester, for example, glycidyl (meth) acrylic acid, 2-methyl glycidyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3, 4-epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 3,4-epoxytricyclo [4] 5.2.1.0 ^2.6 ] decyl (meth) acrylate, etc .;
Examples of α-alkyl acrylic acid oxiranyl (cyclo) alkyl esters such as glycidyl α-ethyl acrylic acid, glycidyl α-n-propyl acrylic acid, glycidyl α-n-butyl acrylic acid, α-ethyl acrylic acid 6, 7-epoxy Heptyl, α-ethyl acrylic acid 3,4-epoxycyclohexyl etc .;
As a glycidyl ether compound which has a polymerizable unsaturated bond, for example, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether etc .;
As a (meth) acrylic acid ester having an oxetanyl group, for example, 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyl oxetane, 3-((meth) acryloyloxy) Methyl) -2-methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyl oxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloylyl Oxymethyl oxetane, 3-ethyl -3- (meth) acryloyl oxymethyl oxetane etc. can be mentioned, respectively.

Among these specific examples, glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxytricyclo [5.2. 1.0 ^2.6 ] decyl methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, 3-methacryloyloxymethyl-3-ethyl oxetane, 3-methyl-3- Methacryloyloxymethyl oxetane or 3-ethyl-3-methacryloyloxymethyl oxetane is preferred from the viewpoint of polymerizability.

  The compounds (a2) described above can be used alone or in combination of two or more.

  [A] A structural unit having a (meth) acryloyloxy group of a polymer containing a structural unit having a carboxyl group is obtained by reacting a carboxyl group in the polymer with a (meth) acrylic acid ester having an epoxy group. The structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (2).

In the formula ^{(2), R 10} and ^{R 11} are each independently a hydrogen atom or a methyl group. c is an integer of 1 to 6; R ¹² is a divalent group represented by the following formula (2-1) or the following formula (2-2).

In the above formula ^{(2-1), R 13} is a hydrogen atom or a methyl group. * Shows the site | part couple | bonded with an oxygen atom in the said Formula (2-1) and said Formula (2-2).

When a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate is reacted with a copolymer having a carboxyl group for the structural unit represented by the above formula (2), for example, R in formula (2) ¹² is a formula (2-1). On the other hand, when a copolymer having a carboxyl group is reacted with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, R ¹² in the formula (2) becomes the formula (2-2).

  In the reaction of the carboxyl group in the above-mentioned polymer with an unsaturated compound such as (meth) acrylic acid ester having an epoxy group, a heavy catalyst containing a polymerization inhibitor is preferably added, if necessary, in the presence of a suitable catalyst. The unsaturated compound having an epoxy group is charged into the combined solution, and the mixture is stirred for a predetermined time under heating. Examples of the catalyst include tetrabutyl ammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 hours to 12 hours.

The content of the structural unit having (A2) (meth) acryloyloxy group in the polymer containing the structural unit having [A] carboxyl group is 10 mol% to 70 mol% of all the components of [A] polymer It is preferable that there be 20 mol% to 50 mol%.

  When the content of the structural unit having a (meth) acryloyloxy group is less than 10 mol%, the sensitivity of the radiation sensitive resin composition of the present embodiment to radiation tends to decrease, and the obtained cured film The heat resistance of is also not sufficient. Further, when the content is more than 70% by mole, it causes the development failure at the time of development, and the development residue is easily generated.

  Examples of the compound (a3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) And acryloyloxypropyltriethoxysilane etc. can be mentioned.

  The compounds (a3) described above can be used alone or in combination of two or more.

As the above compound (a4), for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, Mention may be made of (meth) acrylic esters having an oxygen-containing five-membered ring or an oxygen-containing six-membered ring, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds. Specific examples thereof include (meth) acrylic acid alkyl esters such as methyl acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, Meta) acrylic acid sec-butyl, (meth) acrylic acid t-butyl and the like;
As (meth) acrylic acid cycloalkyl ester, for example, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^{2, 6} ] decane-8 -Yl, (meth) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl, isoboronyl (meth) acrylate and the like;
Examples of (meth) acrylic acid aryl esters such as phenyl acrylate and the like;
Examples of (meth) acrylic acid aralkyl ester include, for example, benzyl (meth) acrylate and the like;
As unsaturated dicarboxylic acid dialkyl ester, for example, diethyl maleate, diethyl fumarate etc .;
Examples of (meth) acrylic acid esters having an oxygen-containing five-membered heterocyclic ring or a six-membered oxygen-containing heterocyclic ring include tetrahydrofuran-2-yl (meth) acrylate, tetrahydropyran-2-yl (meth) acrylate, ) Acrylic acid 2-methyltetrahydropyran-2-yl and the like;
As a vinyl aromatic compound, for example, styrene, α-methylstyrene and the like;
As a conjugated diene compound, for example, 1,3-butadiene, isoprene and the like;
Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and the like.

Among the compounds (a4) mentioned above, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methyl glycidyl methacrylate, benzyl methacrylate, tricyclo methacrylate [5.2.1.0 ^{2, 6} Preferred are decane-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like.

  The compounds (a4) can be used alone or in combination of two or more.

  The polymer containing a structural unit having a preferred [A] carboxyl group in the present embodiment is a copolymer of a mixture of polymerizable unsaturated compounds containing the compounds (a1) to (a4) as described above in the following proportions: It can be synthesized by polymerization.

Compound (a1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more preferably 5 mol% to 15 mol%
Compound (a2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%
Compound (a3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%
Compound (a4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%
It is preferable to use in the range of

  The radiation sensitive resin composition of the third embodiment of the present invention has a structural unit having a carboxyl group, which is obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing each compound in the above range. By containing the polymer, high resolution can be achieved without loss of good coatability, so that a cured film having a highly balanced property can be provided even with a high definition pattern. And is preferable.

  [A] The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) of the polymer containing a structural unit having a carboxyl group is preferably 2,000 to 100,000. More preferably, it is 5000-50000. By using a polymer containing a structural unit having [M] carboxyl group having Mw in this range, high resolution can be achieved without loss of good coatability, so even a high definition pattern It is possible to provide a cured film having a highly balanced property.

  The polymer containing a structural unit having a [A] carboxyl group in the radiation sensitive resin composition of the third embodiment of the present invention is preferably a mixture of polymerizable unsaturated compounds as described above, preferably in a suitable solvent. And preferably by polymerization in the presence of a radical polymerization initiator.

  Examples of the solvent used for the above polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl Ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol etc. can be mentioned. These solvents can be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2 '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Mention may be made of azo compounds such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used alone or in combination of two or more.

<[B] Radiation-sensitive compound>
The radiation sensitive compound [B] imparts radiation sensitive properties to the radiation sensitive composition. This [B] radiation sensitive compound is a compound which produces a reactive active species upon exposure to radiation. Here, radiation includes at least visible light, ultraviolet light, far ultraviolet light, electron beam (charged particle beam) and X-ray. As the radiation sensitive compound (B), (B1) an acid generator, (B2) a polymerization initiator or a combination thereof is preferable. (B1) When an acid generator is used, it can be made into either a positive type or a negative type radiation sensitive composition depending on other additive components. When a quinone diazide compound is used, it can be set as a positive type radiation sensitive composition. On the other hand, when (B2) polymerization initiator is used, it can be set as a negative type radiation sensitive composition.

((B1) acid generator)
(B1) The acid generator is a compound which generates an acid upon irradiation with radiation. The radiation sensitive resin composition of the present embodiment can exhibit, for example, positive type radiation sensitive characteristics with respect to an alkaline developer by containing the acid generator (B1).

  The acid generator (B1) is not particularly limited as long as it is a compound that generates an acid (eg, carboxylic acid, sulfonic acid, etc.) upon irradiation with radiation. Examples of the acid generator (B1) include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, quinone diazide compounds and the like. Among these, quinone diazide compounds are preferred.

(Quinone diazide compounds)
The quinone diazide compound generates a carboxylic acid upon irradiation with radiation. As the quinone diazide compound, for example, a condensation product of a phenolic compound or an alcoholic compound (hereinafter, also referred to as "mother core") and 1,2-naphthoquinone diazide sulfonic acid halide can be used.

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

  Examples of trihydroxybenzophenones include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like.

  Examples of tetrahydroxybenzophenones include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, 3,4,2'-tetrahydroxy-4'-methyl benzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxy benzophenone etc. are mentioned.

  Examples of pentahydroxybenzophenones include 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like.

  Examples of hexahydroxybenzophenones include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like.

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tri (p-) Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5- Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobie Den -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  As another mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [1- [1 4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl)- 4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene and the like.

  Among these mother nuclei, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- [1- [1 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  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. Among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

  The synthesis of the quinone diazide compound can be carried out by a known condensation reaction. In this condensation reaction, 1,2-naphthoquinonediazide sulfone preferably corresponds to 30 mol% or more and 85 mol% or less, that is, 30 mol% to 85 mol%, with respect to the number of OH groups in the phenolic compound or the alcoholic compound. An acid halide can be used.

  In addition, as the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2-naphtho Quinonediazide-4-sulfonic acid amide and the like are also suitably used.

  These quinonediazide compounds can be used alone or in combination of two or more. The quinonediazide compound can also be used in combination with an oxime sulfonate compound, an onium salt, a sulfone imide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound or the like.

  The lower limit of the content of the acid generator (B1) in the radiation sensitive resin composition of the present embodiment is preferably 5 parts by mass, more preferably 10 parts by mass with respect to 100 parts by mass of the polymer [A]. 20 parts by mass is more preferred. On the other hand, as this upper limit, 80 mass parts is preferred, 60 mass parts is more preferred, and 40 mass parts is still more preferred. By setting the content of the acid generator (B1) in the above range, it is possible to increase the difference in solubility between a portion irradiated with radiation and a portion not irradiated with radiation in the developer and to improve patterning performance. In addition, the solvent resistance of the insulating film can be made favorable.

((B2) polymerization initiator)
The polymerization initiator (B2) is a component that generates an active species capable of initiating polymerization of a polymerizable compound in response to radiation. The radiation sensitive resin composition of the present embodiment can exhibit, for example, a negative type radiation sensitive property to an alkaline developer by containing the (B2) polymerization initiator. As a polymerization initiator (B2), a radical photopolymerization initiator can be mentioned. As this photo radical polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound etc. are mentioned, for example. These compounds can be used 1 type or in mixture of 2 or more types.

(O-acyloxime compound)
As an O-acyloxime compound, for example, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyl] Oxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl] -9. H. -Carbazol-3-yl] -octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] } -9. H. And -carbazol-3-yl] -1- (O-acetyloxime) and the like.

(Acetophenone compound)
As an acetophenone compound, an alpha-amino ketone compound, an alpha-hydroxy ketone compound, etc. are mentioned, for example.

(Α-Amino Ketone Compound)
Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4). And -morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.

(Α-hydroxy ketone compound)
As the α-hydroxy ketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone.

(Biimidazole compound)
As a biimidazole compound, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,2, 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

  The content of the (B2) polymerization initiator in the radiation sensitive resin composition of the present embodiment can be, for example, 1 to 40 parts by mass with respect to 100 parts by mass of the polymer [A]. By setting the content of the polymerization initiator (B2) in such a range, the radiation sensitive resin composition of the present embodiment has high solvent resistance, hardness and adhesiveness even with a low exposure amount. An insulating film can be formed.

[C] Polymerizable unsaturated compound [C] The polymerizable unsaturated compound in the radiation sensitive resin composition of the third embodiment of the present invention irradiates radiation in the presence of the above-mentioned [B] radiation sensitive compound It is an unsaturated compound which is polymerized by Such a [C] polymerizable unsaturated compound is not particularly limited, but, for example, monofunctional, bifunctional or trifunctional or higher functional (meth) acrylic acid ester has good polymerizability, And it is preferable from the point which the intensity | strength of the insulating film formed and a spacer base improves.

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, (2- (meth) acryloyloxyethyl) (2-hydroxypropyl) phthalate, Examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate and the like. As commercially available products of these, under the trade name, for example, ALONIX (registered trademark) M-101, M-111, M-114, M-5300 (all manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) Trademarks TC-110S and TC-120S (all manufactured by Nippon Kayaku Co., Ltd.); Biscoat 158 and 2311 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

  As said bifunctional (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol diacrylate, tetraethylene glycol di (meth), for example Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate etc. can be mentioned. As commercially available products of these, under the trade name, for example, ALONIX (registered trademark) M-210, M-240, M-6200 (all manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) HDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.), Viscote 260, 312, 335 HP (above, Osaka Organic Chemical Industry Co., Ltd.), light acrylate 1,9-NDA (Kyoeisha Co., Ltd.) Chemical Co., Ltd. product etc. can be mentioned.

Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Dipentaerythritol hexa (meth) acrylate;
A mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate;
Ethylene oxide modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, succinic acid modified pentaerythritol tri (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, tri Pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a mixture of isocyanuric acid EO modified diacrylate and isocyanuric acid EO modified triacrylate;
A compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and one, three or more hydroxyl groups in the molecule and three, four or five (meth) acryloyloxy compounds The polyfunctional urethane acrylate type compound etc. which are obtained by making it react with the compound which has group can be mentioned.

  As a commercial item of (meth) acrylic acid ester of the above-mentioned trifunctional or higher, under the trade name, for example, Alonix (registered trademark) M-309, M-400, M-405, M-450, M- M-7030, M-8030, M-80060, TO-1450 (all available from Toagosei Co., Ltd.), KAYARAD (registered trademark) TMPTA, DPHA, DPCA-20, DPCA-30, DPCA -60, DPCA-120, DPEA-12 (above, Nippon Kayaku Co., Ltd.), Viscote 295, 300, 360, GPT, 3 PA, 400 (above, Osaka Organic Chemical Industry (stock) New Frontier (registered trademark) R-1150 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), KAYARAD (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and commercial products containing a polyfunctional urethane acrylate compound. Recording trademark) DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Among these, particularly, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate ;
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;
Mixtures of tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate;
Commercially available products containing ethylene oxide-modified dipentaerythritol hexaacrylate, polyfunctional urethane acrylate compounds, succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylate are preferable.

  The above [C] polymerizable unsaturated compounds can be used alone or in combination of two or more.

  The use ratio of the [C] polymerizable unsaturated compound in the radiation sensitive resin composition of the third embodiment of the present invention is preferably 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the [A] polymer. It is more preferably 50 parts by mass to 200 parts by mass. [B] By setting the use ratio of the polymerizable unsaturated monomer in the above range, a cured film can be formed with high resolution without causing a problem of development residual, which is preferable.

(Other optional ingredients)
The radiation sensitive resin composition of the third embodiment of the present invention may be added to a polymer containing a structural unit having a carboxyl group [A] and a radiation sensitive compound [B] or a structure having a carboxyl group [A] In addition to the unit-containing polymer, the [B] radiation-sensitive compound, and the [C] polymerizable unsaturated compound, other optional components can be contained as needed, as long as the effects of the present invention are not impaired. Examples of other optional components that can be used here include [D] adhesion assistant, [E] surfactant, and [F] polymerization inhibitor. Other optional components may be used as a mixture of two or more. Each optional component is described below.

[D] Adhesion assistant The above-mentioned adhesion assistant [D] can be used to further improve the adhesion between the formed cured film and the substrate. As such a [D] adhesion aiding agent, the same one as the above-mentioned compound (a3) can be used, and trimethoxysilylbenzoic acid, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane etc. can be used. The use ratio of the [D] adhesion assistant in the radiation sensitive resin composition of the present embodiment is preferably 20 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the [A] polymer. It is 10 parts by mass. [D] By setting the content ratio of the adhesion aiding agent in the above range, the adhesion between the formed cured film and the substrate is effectively improved.

[E] Surfactant As said [E] surfactant, a fluorochemical surfactant, a silicone type surfactant, etc. can be mentioned, for example. The use ratio of the [E] surfactant in the radiation sensitive resin composition of the present embodiment is preferably 1 part by mass or less, more preferably 0.01 part by mass with respect to 100 parts by mass of the [A] polymer. Part to 0.6 parts by mass.

[F] Polymerization Inhibitor The above-mentioned [F] polymerization inhibitor captures a radical generated by exposure or heating, or cleaves a molecule of the [A] polymer by decomposing a peroxide generated by oxidation. It is an ingredient to suppress. By containing the [F] polymerization inhibitor in the radiation-sensitive resin composition of the present embodiment, cracking and deterioration of polymer molecules in the cured film to be formed can be suppressed. For example, light resistance can be improved.

  As such [F] polymerization inhibitors, for example, hindered phenol compounds, hindered amine compounds, alkyl phosphite compounds, thioether compounds etc. may be mentioned, and among these, hindered phenol compounds are preferably used. Can.

  Examples of the above hindered phenol compounds include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -Isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diyl bis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 3,3 ' 3 ', 5', 5'-hexa-tert-butyl-a, a '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -O-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- [4,6-bis (octylthio) -1,3,6 5-to Azine-2-ylamine] phenol and the like.

  Examples of these commercially available products include Adekastab (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, and AO. -330 (above, manufactured by ADEKA Co., Ltd.), sumilizer (registered trademark) GM, GS, MDP-S, BBM-S, WX-R, GA-80 (all, Sumitomo Chemical Co., Ltd.) IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425 WL, 1520 L, 245, 259, 3114, 565, IRGAMOD 295 (all, BASF) Products), Yoshinox (registered trademark) BHT, BB, 2246G, 425, 250, 930, SS, TT, 917, 314 , Mention may be made of the (stock) by API manufactured by Eye Corporation), and the like.

  As [F] polymerization inhibitors in the present embodiment, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris- (3,5-di) as described above are used. It is preferred to use one or more selected from the group consisting of -tert-butyl-4-hydroxybenzyl) -isocyanurate.

  The content ratio of the polymerization inhibitor [F] is preferably 10 parts by mass or less with respect to 100 parts by mass of the polymer [A], and more preferably 0.1 parts by mass to 5 parts by mass. By setting the content ratio in this range, it is possible to effectively suppress the cleavage and deterioration of the cured film without inhibiting the effect of the present invention.

(Preparation of radiation sensitive resin composition)
Next, preparation of the radiation sensitive resin composition of the third embodiment of the present invention will be described.

  The radiation sensitive resin composition of the third embodiment of the present invention may be added to a polymer containing a structural unit having a carboxyl group [A] and a radiation sensitive compound [B] or a structure having a carboxyl group [A] In addition to the polymer containing the unit, the [B] radiation sensitive compound and the [C] polymerizable unsaturated compound, it is prepared by mixing other optional components such as a [E] surfactant as needed. At this time, an organic solvent can be used to prepare a liquid radiation sensitive resin composition. The organic solvents can be used alone or in combination of two or more.

  Examples of the function of the organic solvent include adjusting the viscosity of the radiation sensitive resin composition and the like to improve the coatability on a substrate and the like, as well as improving the operability and the formability. The viscosity of the radiation sensitive resin composition realized by the inclusion of an organic solvent etc. is, for example, preferably 0.1 mPa · s to 50000 mPa · s (25 ° C.), more preferably 0.5 mPa · s to 10000 mPa · s. s (25 ° C.).

  As an organic solvent which can be used for the radiation sensitive resin composition of 3rd Embodiment of this invention, while dissolving or disperse | distributing other containing components, the thing which does not react with other containing components can be mentioned.

  For example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene Esters such as glycol monoethyl ether acetate and methyl 3-methoxy propionate; polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethers such as propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether; benzene, Aromatic hydrocarbons such as toluene and xylene; Chill acetamide, etc. amides such as N- methylpyrrolidone.

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

  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.

Synthesis Example 1
<Synthesis (1) of Polymer ([A] Polymer) Containing Structural Unit Having [[A] Carboxyl Group>
In a flask equipped with a condenser and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate are charged, followed by 55 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate And 2 parts by mass of α-methylstyrene dimer as a molecular weight modifier, and while gently stirring, raise the temperature of the solution to 80 ° C., hold this temperature for 4 hours, and then raise it to 100 ° C., Polymerization was carried out by maintaining the temperature for 1 hour to obtain a solution containing a copolymer. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor are added to a solution containing the copolymer, and the mixture is stirred at 90 ° C. for 30 minutes in an air atmosphere, and then methacrylic. The polymer (A-1) was obtained by adding 74 mass parts of acid glycidyl, and making it react at 90 degreeC for 10 hours (solid content concentration = 35.0%). The weight average molecular weight Mw of the polymer (A-1) was 9000.

Synthesis Example 2
<Synthesis of Polymer ([A] Polymer) Containing Structural Unit Having [[A] Carboxyl Group (2)>
In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate are charged, and further 18 parts by mass of methacrylic acid, tricyclo methacrylate [5.2] .1.0 ^2.6 ] After charging 25 parts by mass of decane-8-yl, 5 parts of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane, and 32 parts by mass of glycidyl methacrylate, the mixture is purged with nitrogen and then gently stirred. The temperature of the solution was then raised to 80.degree. The temperature was maintained for 5 hours and polymerization was performed to obtain a solution containing 28.8% by mass of the polymer (A-2). Mw of this polymer (A-2) was 12000.

Example 1
<Preparation of negative radiation-sensitive resin composition>
100 parts by mass in terms of solid content of the solution containing the polymer (A-1) obtained in the above Synthesis Example 1 as [A] polymer, and the following (B) as a polymerization initiator as a radiation sensitive compound: B-1) 10 parts by mass, 100 parts by mass of the following (C-1) as a [C] polymerizable unsaturated compound are mixed, and propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration becomes 30% by mass The reaction mixture was filtered through a Millipore filter with a pore size of 0.5 μm to prepare a radiation sensitive resin composition of Example 1.

Example 2
<Preparation of positive-working radiation-sensitive resin composition>
100 parts by mass, in terms of solid content, of the solution containing the polymer (A-2) obtained in the above Synthesis Example 2 as the polymer [A], and the following (B) as the quinone diazide compound as the radiation sensitive compound [B] -2) 30 parts by mass is mixed, propylene glycol monomethyl ether acetate is added as a solvent so that the solid content concentration becomes 30% by mass, and then filtration is carried out using a 0.5 μm pore diameter Millipore filter. A radiation sensitive resin composition was prepared.

  The detail of each component used in Example 1 and Example 2 is shown below.

[B] Radiation-sensitive compound B-1: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE (registered trademark) OXE01, manufactured by BASF AG)
B-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol)

[C] Polymerizable unsaturated compound C-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[Example 3]
<Manufacture and evaluation of liquid crystal display element>
The liquid crystal display element of the present embodiment is an active matrix FFS mode liquid crystal display element. The liquid crystal display element of the present embodiment has the same structure as the liquid crystal display element 10 which is an example of the first embodiment of the present invention described with reference to FIGS.

  The liquid crystal display device of this example manufactures a TFT substrate on which a TFT and an insulating film are formed, manufactures an opposite substrate on which a color filter and a spacer are formed, and then holds a liquid crystal between the substrates according to a liquid crystal dropping method. Manufactured by sealing.

  First, a TFT substrate was manufactured according to a known method and a method described in Patent Document 1. That is, a common electrode by ITO, a common wiring by chromium (Cr) overlapping the common electrode, and a scanning signal line are sequentially formed on a glass substrate having a thickness of 0.7 mm, and then the scanning signal line and the common electrode are formed. After forming a gate insulating film made of silicon nitride to cover, a TFT was formed on the scanning signal line.

  Next, a coating of the radiation sensitive resin composition was formed on the TFT substrate using the radiation sensitive composition prepared in Example 1, and the coating was then irradiated with radiation using a halftone mask. . Then, the coating film irradiated with radiation was developed, and the coating film after development was heated to form a passivation film having a spacer pedestal and a penetrating contact hole formed in a predetermined area. Thereafter, a common electrode made of ITO was formed on the passivation film.

Next, as an alignment agent containing a radiation-sensitive polymer having a photoalignment group, a liquid crystal alignment agent A-1 described in Example 6 of WO 2009/025386 pamphlet is spinnered on a TFT substrate by using a spinner. It applied. Next, after prebaking on a hot plate at 80 ° C. for 1 minute, the film was heated at 180 ° C. for 1 hour in an oven purged with nitrogen inside to form a coating film of an alignment agent with a film thickness of 80 nm. Then, using a Hg-Xe lamp and a Glan-Taylor prism, this coated film surface is irradiated with polarized ultraviolet light 200 J / m ² containing a 313 nm emission line from a direction inclined 40 ° to the direction perpendicular to the substrate surface, A TFT substrate having a photo alignment film was manufactured.

  Next, a counter substrate was manufactured according to a known method and Patent Document 1. On the opposing substrate, a spacer was formed on the overcoat film covering the color filter and the black matrix, and the spacer had a tapered shape and a height of about 4.2 μm. The alignment film of the opposing substrate was formed by the same method as the above-mentioned TFT substrate.

  Next, the manufactured TFT substrate and the opposite substrate were bonded to each other to seal a liquid crystal. That is, an annular seal material was applied to the outer peripheral portion of the display area of the counter substrate, and liquid crystal was dropped on the area surrounded by the seal material, and then bonding with the TFT substrate was performed. The liquid crystal used was a nematic liquid crystal composition having a positive dielectric anisotropy Δε and a refractive index anisotropy Δn of 0.075. The thickness of the liquid crystal (cell gap) was 4.2 μm, which was almost the same as the height of the spacer.

  Next, it bonded together using a pair of polarizing plates. Then, a first drive circuit, a second drive circuit, a control circuit, a backlight, and the like were connected to form a module, and a liquid crystal display element was manufactured.

  Next, a lighting test was performed using the manufactured liquid crystal display element. As a result, it was found that the manufactured liquid crystal display device was capable of uniform black display with low luminance and no display unevenness. Furthermore, using the manufactured liquid crystal display element, external pressure was temporarily applied to the display area from the outside, and the state of the generated display disturbance was visually observed. As a result, immediately after the application of pressure, although the display was disturbed due to the disturbance of liquid crystal alignment, it was found that the degree was slight. Also, it was found that when the application of pressure from the outside was stopped, the disturbance of the display was quickly resolved, and the display was restored to the original display state before the application of pressure.

  Next, a liquid crystal display element is manufactured using the radiation sensitive composition prepared in Example 2 and the radiation sensitive composition prepared in Example 1 described above, and the lighting test is performed. went. As a result, the liquid crystal display device manufactured using the radiation sensitive composition prepared in Example 2 has low luminance and display unevenness as in the case of using the radiation sensitive composition prepared in Example 1 described above. It has been found that a uniform black display without the light is possible. Further, using the liquid crystal display element, external pressure was temporarily applied to the display area from the outside, and the state of the generated display disturbance was visually observed. As a result, as in the case of using the radiation sensitive composition prepared in Example 1 described above, immediately after the application of pressure, although the disturbance of the display due to the disturbance of the liquid crystal alignment occurs, the extent is slight all right. Also, it was found that when the application of pressure from the outside was stopped, the disturbance of the display was quickly resolved, and the display was restored to the original display state before the application of pressure.

  The liquid crystal display element of the present invention is a liquid crystal display element having an excellent image quality based on the thickness of the liquid crystal uniformly controlled. Therefore, the liquid crystal display element of the present invention can be suitably used as a display of a portable electronic device such as a smartphone or a large liquid crystal TV for which a display with excellent image quality is strongly required.

1, 10, 1001 Liquid Crystal Display Elements 2, 1002 First Substrate 3, 1003 Second Substrate 4, 204 Spacer 5, 1005 Insulating Film 6, 114 Spacer Base 7, 1007 Contact Hole 32 First Drive Circuit 33 Second Drive circuit 34 control circuit 35 back light 36 scanning signal line 37 video signal line 38 display area 39 common wiring 40 liquid crystal 41 common electrode 42 pixel electrode 43 TFT
DESCRIPTION OF SYMBOLS 100 TFT substrate 103 gate insulating film 104 semiconductor layer 105 drain electrode 106 source electrode 107 passivation film 109 contact hole 113 alignment film 120, 220 polarizing plate 200 opposing substrate 201 black matrix 202 color filter 203 overcoat film 361 conductive film 362 metal film 1004 Main spacer 1014 Secondary spacer

Claims (7)

A plurality of spacers disposed on the second substrate of the first substrate and the second substrate disposed opposite to each other;
An insulating film is provided on the first substrate, and a spacer pedestal is provided on at least one of the portions of the insulating film facing the tip of the spacer,
It is a manufacturing method of a liquid crystal display element which sandwiches a liquid crystal between the 1st substrate and the 2nd substrate via an orientation film of at least one layer,
(1) a coating film forming step of forming a coating film of a radiation sensitive resin composition on the first substrate,
(2) an exposure step of irradiating the coating film with radiation using at least one selected from a halftone mask and a gray tone mask;
(3) developing the coating film irradiated with the radiation, and (4) heating the heated coating film.
The radiation sensitive resin composition is
[A] A polymer having a crosslinkable group which is at least one selected from the group consisting of an oxetanyl group and an oxynyl group, and further comprising a structural unit having a carboxyl group, and [B] a radiation sensitive compound And
A method of manufacturing a liquid crystal display device, comprising: collectively forming an insulating film having the spacer pedestal on the first substrate. In the (2) exposure step, radiation is irradiated using at least one selected from the halftone mask and the gray tone mask, and the coating film of the radiation sensitive resin composition has at least two different radiation doses. Provide one part,
By the (3) developing step and the (4) heating step, one of the two parts of the (2) exposure step forms the insulating film and the spacer pedestal disposed thereon. The method according to claim 1, wherein another portion forms the insulating film. [A] The polymer containing a structural unit having a carboxyl group is a polymer further having a structural unit represented by the following formula (1): The liquid crystal display device according to claim 1 or 2, Method.
(In formula (1), R 1 is a hydrogen atom or a methyl group, R 2, R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and an alkoxy group having 1 to 6 carbon atoms Represents any of the following: n represents an integer of 1 to 6) A plurality of spacers are provided on the second substrate of the first substrate and the second substrate disposed opposite to each other, and an insulating film is provided on the first substrate, and the spacer on the insulating film is provided. A liquid crystal display element having a spacer pedestal on at least one of the parts facing the tip of the liquid crystal and sandwiching liquid crystal between the first substrate and the second substrate with at least one alignment film interposed therebetween. A radiation-sensitive resin composition used for collectively forming the insulating film and the spacer pedestal by irradiation with radiation using at least one selected from a halftone mask and a gray tone mask,
[A] A polymer having a crosslinkable group which is at least one selected from the group consisting of an oxetanyl group and an oxynyl group, and further comprising a structural unit having a carboxyl group, and [B] a radiation sensitive compound Radiation-sensitive resin composition characterized in that. The radiation-sensitive resin composition according to claim 4, wherein the polymer containing a structural unit having a carboxyl group [A] is a polymer further having a structural unit represented by the following formula (1).
(In formula (1), R 1 is a hydrogen atom or a methyl group, R 2, R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and an alkoxy group having 1 to 6 carbon atoms Represents any of the following: n represents an integer of 1 to 6) [B] The radiation sensitive resin composition according to claim 4 or 5, wherein the radiation sensitive compound is an acid generator, a polymerization initiator or a combination thereof. A plurality of spacers disposed on the second substrate of the first substrate and the second substrate disposed opposite to each other;
An insulating film is provided on the first substrate, and a spacer pedestal is provided on at least one of the portions of the insulating film facing the tip of the spacer,
A liquid crystal display element formed by sandwiching a liquid crystal between at least one layer of an alignment film between the first substrate and the second substrate,
A liquid crystal display device characterized in that the insulating film on the first substrate and the spacer pedestal on the insulating film are collectively formed by the following steps (1) to (4).
(1) a coating film forming step of forming a coating film of a radiation sensitive resin composition on the first substrate (2) radiation is applied to the coating film using at least one selected from a halftone mask and a gray tone mask An exposure step of irradiating (3) a developing step of developing the coating film irradiated with the radiation (4) a heating step of heating the developed coating film, wherein the radiation sensitive resin composition comprises
[A] A polymer having a crosslinkable group which is at least one selected from the group consisting of an oxetanyl group and an oxynyl group, and further comprising a structural unit having a carboxyl group, and [B] a radiation sensitive compound It is a thing.