KR20160102116A - Manufacturing method for liquid crystal display device, radiation-sensitive resin composition and liquid crystal display device - Google Patents

Abstract

Provided are a manufacturing method for a liquid crystal display device having less unevenness in height of a spacer which has steps, a radiation-sensitive resin composition used thereto, and a liquid crystal display device. The liquid crystal display device (10) includes: a first substrate (2) and a second substrate (3) which are facing each other; a plurality of spacers (4) disposed on the second substrate (3); an insulation film (5) disposed on the first substrate (2); at least one spacer pedestal (6) disposed on the insulation film (5) at a part facing a front end of the spacer; and a liquid crystal interposed between the first substrate (2) and the second substrate (3). The insulation film (5) disposed on the first substrate (2) and the spacer pedestal (6) disposed on the insulation film (5) are collectively and integrally formed by using the radiation-sensitive resin composition, when forming the insulation film (5) through patterning such that the insulation film (5) has a contact hole (7) and a desired shape.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal display device, a method of manufacturing the same, a method of manufacturing the same, a method of manufacturing the liquid crystal display device,

The present invention relates to a method for producing a liquid crystal display element, a radiation-sensitive resin composition and a liquid crystal display element.

The liquid crystal display element has a structure in which liquid crystal is sandwiched between a pair of substrates arranged opposite to each other. An electrode can be formed on these substrates, and an alignment film can be formed on the surface of each substrate for the purpose of controlling the alignment of the liquid crystal. Further, these pair of substrates are held by, for example, a pair of deflection plates. Then, when an electric field is applied between the substrates, the liquid crystal is driven to change orientation, and light is partially transmitted or shielded. In a liquid crystal display element, an image is displayed using these characteristics. Such a liquid crystal display device is advantageous in that it can be made thinner and lighter in weight as compared with a conventional CRT-type display device.

In a liquid crystal display device, various liquid crystal modes in which an initial alignment state of liquid crystal and an orientation change operation are different are known. For example, a liquid crystal mode 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 originally developed was used as a display element of an electronic calculator or a clock, centering on a character display. Thereafter, the development of the simple matrix method has facilitated dot matrix display, thereby expanding its use as a display element of a notebook computer or the like. Subsequently, by developing an active matrix in which a thin film transistor (TFT: Thin Film Transistor) for each pixel is arranged, it has become possible to realize a good image quality excellent in contrast ratio and response performance. Further, the liquid crystal display element overcomes the problems such as high definition, colorization, and wide viewing angle, and is also used for a monitor of a desktop computer. In recent years, a wider viewing angle, faster response of the liquid crystal, improvement of display quality, and the like have been realized and are used as display devices for portable electronic devices such as a large-sized thin display device for a television or a smartphone requiring high- Is coming.

In recent years, such a liquid crystal display device has been required to have a higher image quality in accordance with the expansion of applications as described above. Particularly, in a display of a medical instrument or a liquid crystal television, a black display is very important, and a liquid crystal display device which is capable of performing uniform black display with low luminance and display irregularity is strongly demanded.

As described above, the liquid crystal display element has a structure in which liquid crystal is sandwiched between a pair of substrates arranged opposite to each other, and the display region is composed of a plurality of pixels. In order to achieve a uniform black display and realize a high quality image, it is important to uniformize the thickness (cell gap) of the liquid crystal in each pixel.

As a method of making the thickness of the liquid crystal between the substrates uniform in the liquid crystal display element, there are, for example, a method of disposing a bead spacer as a spherical spacer member between a pair of substrates, And a method of forming a columnar protruding spacer on one of the substrates is known. Particularly, in a liquid crystal display element which realizes a high-quality picture quality by enabling uniform black display, a method of forming a columnar spacer on either one of a pair of substrates is used (for example, refer to Patent Document 1 ).

Japanese Laid-Open Patent Publication No. 2010-152188

In a liquid crystal display device, for example, in order to cope with the increase in size, a manufacturing method using a liquid crystal dropping method is effective. In the liquid crystal dropping method, a liquid crystal is dropped onto one of a pair of substrates prepared and then bonded to the other substrate, so that the liquid crystal can be interposed between the pair of substrates.

In the case of a liquid crystal display element having a spacer constituting the above-described columnar phase, a structure for forming a step on the spacer is known. That is, by forming the spacer formed on the substrate with, for example, two kinds of spacers having different heights, it is possible to form a step on the spacer. The structure for forming the step on the spacer is particularly effective for the liquid dropping method described above.

In the production of a liquid crystal display device, when a step is formed on a spacer on a substrate, a pair of substrates are bonded to each other so that the spacer does not contact the surface of the opposing substrate. That is, some of the plurality of spacers on the substrate have gaps formed between the tips thereof and the surface of the counter substrate. In a liquid crystal display device provided with such a spacer, it is easy to align the substrate by liquid crystal drop method during the manufacturing process, and the margin of the bonding process of the substrate can be widened.

In a liquid crystal display element having a structure in which a step is formed in a spacer, a spacer formed higher than the spacer in normal use functions to ensure uniformity of the cell gap. That is, the spacers whose tips are brought into contact with the surface of the opposing substrate improve the uniformity of cell gaps. On the other hand, when pressure such as pressure is externally applied to the liquid crystal display element, a spacer formed to be lower than the spacer also functions as a support for the substrate. That is, the spacer formed so as to form the gap between the opposed substrate and the opposed substrate also acts as the support of the substrate, and fluctuation of the cell gap can be suppressed and the external pressure resistance can be improved.

The spacer having such a stepped portion can be formed by patterning using a photosensitive spacer forming member. In this case, it is possible to form a plurality of kinds of spacers having different heights by, for example, lowering the mask opening in a part of the mask for patterning or forming a light shielding film having an arbitrary transmittance when exposing the spacer forming member.

However, it is difficult to form the spacers formed with the steps in the above-described manner, particularly in the case of a plurality of spacers formed at a lower height, in a uniform height. Further, the spacers formed at lower heights tend to cause unevenness in the height on the substrate, which may cause a reduction in the yield at the time of substrate bonding in the production of liquid crystal display elements.

Further, in recent years, as described above, in a liquid crystal display element, a pixel is becoming finer and more refined. Therefore, when a spacer is to be formed on a substrate as a pattern having a fixed size, a spacer having a stepped portion has a problem in that the height of the spacer having a smaller height is increased.

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 uneven height of the spacer is small and a step is formed in the spacer.

It is also an object of the present invention to provide a radiation-sensitive resin composition for use in the production of a liquid crystal display element in which height unevenness of the spacer is small and a step is formed in the spacer.

It is also an object of the present invention to provide a liquid crystal display element in which height unevenness of the spacer is small and a step is formed in the spacer.

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

According to a first aspect of the present invention, there is provided a plasma display panel comprising a first substrate and a second substrate arranged opposite to each other and having a plurality of spacers on the second substrate,

A spacer having a spacer base on at least one portion of the insulating film on the insulating substrate opposite to the tip of the spacer,

And a liquid crystal interposed between the first substrate and the second substrate, the method comprising:

(1) a coating film forming step of forming a coating film of the 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 method for manufacturing a liquid crystal display element having a heating step of heating the developed coating film, wherein an insulating film having the spacer pedestal is collectively formed on the first substrate.

In the first aspect of the present invention, in the step (2), the radiation is irradiated using at least one selected from the halftone mask and the gray-tone mask, and the radiation- At least two portions having different dose amounts are formed,

(2) one of the two parts of the exposure step forms the insulating film and the spacer base disposed thereon by the developing step (3) and the heating step (4), and the other part It is preferable to form the insulating film.

In the first aspect of the present invention, the radiation-

[A] a polymer comprising a structural unit having a carboxyl group,

[B] It is preferable to contain a radiation-sensitive compound.

In the first aspect of the present invention, it is preferable that the polymer containing a structural unit having a carboxyl group [A] contained in the radiation sensitive resin composition further has a crosslinkable group.

In the first aspect of the present invention, the cross-linking group of the polymer containing the structural unit having a carboxyl group [A] contained in the radiation sensitive resin composition is preferably an oxetanyl group, an oxiranyl group and a (meth) And at least one member selected from the group consisting of diarrhea.

In the first aspect of the present invention, the polymer containing the structural unit having a carboxyl group as described above in the above-mentioned radiation-sensitive resin composition is preferably a polymer having a structural unit represented by the following formula (1) Do:

(Wherein 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 cycloalkyl group having 3 to 12 carbon atoms, An alkoxy group having 1 to 6 carbon atoms;

and n represents an integer of 1 to 6).

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

A second aspect of the present invention is a semiconductor device having a plurality of spacers on a first substrate and a second substrate disposed on an opposing substrate and having an insulating film on the first substrate, And the spacer base and the spacer base of the liquid crystal display element in which the liquid crystal is sandwiched between the first substrate and the second substrate from the halftone mask and the gray tone mask The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the radiation-

[A] a polymer comprising a structural unit having a carboxyl group,

[B] a radiation-sensitive resin composition.

In the second aspect of the present invention, it is preferable that the polymer comprising the structural unit having a carboxyl group [A] further has a crosslinkable group.

In the second aspect of the present invention, the crosslinkable group possessed by the polymer comprising a structural unit having a carboxyl group [A] is at least one selected from the group consisting of oxetanyl group, oxiranyl group and (meth) acryloyl group It is desirable to be species.

In the second aspect of the present invention, it is preferable that the polymer comprising the structural unit having [A] carboxyl group is further a polymer having a structural unit represented by the following formula (1)

(Wherein 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 cycloalkyl group having 3 to 12 carbon atoms, An alkoxy group having 1 to 6 carbon atoms;

and n represents an integer of 1 to 6).

A third aspect of the present invention is a liquid crystal display device having a plurality of spacers disposed on a first substrate and a second substrate facing each other,

A spacer having a spacer base on at least one portion of the insulating film on the insulating substrate opposite to the tip of the spacer,

And a liquid crystal interposed between the first substrate and the second substrate,

Wherein the insulating film on the first substrate and the spacer base 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 the 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

(4) a heating step of heating the developed coating film

In the third aspect of the present invention, the radiation-

[A] a polymer comprising a structural unit having a carboxyl group,

[B] It is preferable to contain 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 unevenness of the spacer is small and the step is formed in the spacer.

According to the second aspect of the present invention, there is provided a radiation sensitive resin composition for use in the production of a liquid crystal display element in which height unevenness of spacers is small and a step is formed in spacers.

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

1 is a cross-sectional view schematically illustrating a structure of a liquid crystal display element according to a first embodiment of the present invention.
2 is a cross-sectional view schematically illustrating the structure of a conventional liquid crystal display element.
Fig. 3 is a schematic configuration diagram showing an example of the configuration of a liquid crystal display element according to the first embodiment of the present invention.
4 is a schematic circuit diagram illustrating an example of the circuit configuration of a pixel of a liquid crystal display element according to the first embodiment of the present invention.
5 is a plan view schematically illustrating a pixel portion of a liquid crystal display element which is one example of the first embodiment of the present invention.
6 is a cross-sectional view schematically showing a cross-sectional structure taken along the line A-A 'in Fig.

(Mode for carrying out the invention)

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

1, the first substrate 2, the second substrate 3, the spacers 4, the insulating film 5, and the spacers 5 are formed so as to make clear the characteristics of the liquid crystal display element 1 according to the first embodiment of the present invention. Only the pedestal 6 appears, and the other components are omitted for convenience. A contact hole 7 for electrically connecting electrodes (not shown) and the like (not shown) formed on the second substrate 3 is disposed on the insulating film 5 have.

1, a liquid crystal display element 1 according to a first embodiment of the present invention includes a first substrate 2 and a second substrate 3 on the first substrate 2 and a second substrate 3, A plurality of spacers 4 are provided on the side of the substrate 2 and an insulating film 5 is provided on the side of the first substrate 2 on the side of the second substrate 3. The liquid crystal display element 1 also has a spacer pedestal 6 on at least one portion of the insulating film 5 that faces the tip of the spacer 4. The liquid crystal display element 1 is configured by sandwiching liquid crystals (not shown) between the first substrate 2 and the second substrate 3.

In the liquid crystal display element 1 of the first embodiment of the present invention, the spacer pedestal 6 on the insulating film 5 of the second substrate 3 is a part of the insulating film 5 forming the lower layer, And the insulating film 5 when the insulating film 5 is formed. That is, in the liquid crystal display element 1, the insulating film 5 and the spacer pedestal 6 thereon are formed in the contact hole 7 in accordance with the manufacturing method of the liquid crystal display element of the second embodiment of the present invention, And patterning is performed so as to have a desired shape to form the insulating film 5.

In the liquid crystal display element 1 of the first embodiment of the present invention, the plurality of spacers 4 are formed to have the same uniform height on the second substrate 3, respectively. Then, in a part of the spacer 4, its tip is in contact with 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 spacer 4 in which the spacer pedestal 6 is not formed on the other part of the spacer 4, that is, the part of the first substrate 2 opposite to the insulating film 5, And a gap is formed between the opposed portion.

Therefore, in the liquid crystal display element 1 of the first embodiment of the present invention, the plurality of spacers 4 are formed to have the same height on the second substrate 3, Respectively. At this time, in the liquid crystal display element 1, since each of the plurality of spacers 4 is formed to have the same height, it is easy to reduce the height unevenness of the spacers. That is, the liquid crystal display element 1 according to the first embodiment of the present invention can reduce the height unevenness of the spacer and can form a step on the spacer.

2 is a cross-sectional view schematically illustrating the structure of a conventional liquid crystal display element.

2, in order to clarify the difference in structure from the liquid crystal display element 1 of the first embodiment of the present invention, the first substrate 1002 of the conventional liquid crystal display element 1001, Only the substrate 1003, the main spacer 1004, the auxiliary spacer 1014 and the insulating film 1005 are shown, and other components are omitted for convenience. A contact hole 1007 for electrically connecting an electrode or the like (not shown) disposed on the insulating film 1005 and an electrode (not shown) formed on the second substrate 1003 is also formed in the insulating film 1005 have.

2, the conventional liquid crystal display element 1001 is disposed on the first substrate 1002 side of the second substrate 1003 in the first substrate 1002 and the second substrate 1003 arranged to face each other, And has a main spacer 1004 and a sub spacer 1014 on its surface and an insulating film 1005 on the surface of the first substrate 1002 on the side of the second substrate 1003. 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 formed 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 on the second substrate 1003 so as to be higher than the sub-spacer 1014. The tip of the main spacer 1004 is in contact with a part of the insulating film 1005 opposite to the tip. 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 portion and the opposite portion of the insulating film 1005.

Therefore, in the conventional liquid crystal display element 1001, a step is formed between the main spacer 1004 and the sub-spacer 1014. However, on the other hand, since the auxiliary spacer 1014 has a height different from that of the main spacer 1004 and is formed to be lower, the height is likely to be uneven as described above. As a result, in the liquid crystal display element 1001, there is a fear that the yield of the substrate bonding step may be lowered during its production.

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 spacer 4 can be reduced and the step difference can be formed in the spacer 4 have. As a result, it is different from the conventional liquid crystal display element 1001 of FIG. 2, and it is possible to suppress the lowering of the yield in the substrate bonding step in the production thereof.

Hereinafter, an example of a more detailed structure of the liquid crystal display element 1 of the first embodiment of the present invention will be described using appropriate drawings. Next, the method of manufacturing the liquid crystal display element according to the second embodiment of the present invention and the radiation sensitive resin composition of the third embodiment of the present invention used therefor will be described.

In the present invention, "radiation" irradiated in exposure includes visible light, ultraviolet light, far ultraviolet light, X-ray and charged particle light.

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 type liquid crystal display element or an active matrix type liquid crystal display element. The active matrix type liquid crystal display device is used for displays (monitors) for portable electronic devices, displays for personal computers, displays for printing or design, displays for medical devices, liquid crystal televisions, and the like.

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

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

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

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

3 shows five scanning signal lines 36 connected to the second driving circuit 33 and schematically shows a part of the plurality of scanning signal lines 36. The actual liquid crystal display panel 31 ), A plurality of scanning signal lines 36 are further tightly arranged. 3 shows eight video signal lines 37 connected to the first driving circuit 32. It schematically shows a part of the plurality of video signal lines 37. The liquid crystal display panel 31 ), A plurality of video signal lines 37 are additionally disposed.

The display area 38 for displaying the image of the liquid crystal display panel 31 is formed as a set of a plurality of pixels arranged in a matrix. The area occupied by one pixel in the display area 38 corresponds to an area surrounded by two adjacent scanning signal lines 36 and two adjacent video signal lines 37, for example. 4, and includes a TFT 43, a pixel electrode 42, and a common electrode 41 (an opposing electrode (not shown), which functions as an active element And a liquid crystal 40, as shown in Fig. In the liquid crystal display panel 31, as shown in Fig. 4, for example, a common wiring 39 for commoning the common electrodes 41 of a plurality of pixels is formed.

The liquid crystal display panel 31 includes a TFT substrate (not shown in Figs. 3 and 4) on which the TFT 43 is formed, which is an example of the first substrate 2 in Fig. 1, 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 adhered with an annular sealing material (not shown in Figs. 3 and 4) formed on the outside of the display region 38, and the liquid crystal 40 is adhered to the TFT substrate, And is sealed in a space surrounded by a sealing material. The liquid crystal display panel 31 of the liquid crystal display element 10 has a pair of polarizing plates (not shown in Figs. 3 and 4) arranged opposite to each other with the TFT substrate, the liquid crystal 40 and the counter substrate interposed therebetween . The liquid crystal display element 10 has a backlight 35 disposed on the back side opposite to the entire surface side serving as an observer side and emitting light to the liquid crystal display panel 31 from the back side.

The TFT substrate is a substrate on which a scanning signal line 36, a video signal line 37, a TFT 43 as an active element, and a pixel electrode 42 are formed on an insulating substrate such as a glass substrate. When the driving method of the liquid crystal display element 10 is the transverse electric field driving method such as the IPS mode or the FFS mode, the common electrode 41 and the common wiring 39 of the liquid crystal display panel 31 are arranged on the TFT substrate have. When the driving method of the liquid crystal display element 10 is the conventional system driving method such as the VA mode or the TN mode, the common electrode 41 of the liquid crystal display panel 31 is arranged on the counter substrate. In the case of the liquid crystal display element 1 of the previous system driving type, the common electrode 41 of the liquid crystal display panel 31 is a flat electrode of one large-area overall shape shared by all the pixels, (39) is not formed.

In the liquid crystal display element 10, the first driving circuit 32 generates a video signal (also referred to as a gray-scale voltage) added to the pixel electrode 42 of each pixel via the video signal line 37 And is generally referred to as a source driver, a data driver, or the like. The second driving circuit 33 is a driving circuit for generating a scanning signal in addition to the scanning signal line 36 and is generally a driving circuit called a gate driver, a scanning driver, or the like.

The control circuit 34 is a circuit for controlling the operation of the first drive circuit 32, the operation of the second drive circuit 33, and the control of the brightness of the backlight 35, A TFT controller, a timing controller, and the like.

The backlight 35 is a light source such as a fluorescent lamp such as a cold cathode fluorescent lamp or a light emitting diode (LED), and the light emitted from the backlight 35 passes through a reflection plate, a light guide plate, Converted into a planar light beam by a prism sheet or the like, and irradiated to the liquid crystal display panel 31. [

In the liquid crystal display element 10 having the above-described configuration according to the first embodiment of the present invention, the liquid crystal 40 is sandwiched between the TFT substrate and the counter substrate, and a spacer having a columnar shape (Figs. 3 and 4 (Not shown in the drawings). 1, in the liquid crystal display element 10, the thickness of the liquid crystal 40 in each pixel (also referred to as a cell gap) in the sealed space of the liquid crystal 40 A plurality of spacers are provided for uniformizing the thickness of the spacer. In the liquid crystal display element 10, the plurality of spacers are formed on the counter substrate. On the TFT substrate, a spacer pedestal (not shown in Figs. 3 and 4) is formed in a portion of the insulating film opposite to the front end of the spacer.

Hereinafter, the structure of the liquid crystal display element 10, which is an example of the first embodiment of the present invention, particularly, the structure of the pixel of the liquid crystal display panel 31 in which the spacer and the spacer base are formed will be described in more detail.

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

The liquid crystal display element 10 which is one example of the first embodiment of the present invention is a liquid crystal display element of the FFS mode which is a transversal electric field driving system.

Pixels are formed in the matrix-shaped regions surrounded by the scanning signal line 36 and the video signal line 37 in the liquid crystal display element 10 as shown in Fig. In each pixel, a common electrode 41 formed by ITO (Indium Tin Oxide) is formed on the lower side as a whole, and a common electrode 41 for supplying a common potential to the common electrode 41 is formed at the end of the common electrode 41. [ The wirings 39 overlap. On the common electrode 41, there is formed a pixel electrode 42 having a slit sandwiching an insulating film to be described later. When an image signal is supplied to the pixel electrode 42, electric lines of force are generated in the liquid crystal 40 (not shown in FIG. 5) via the slit with the common electrode 41, An image can be formed by rotating the liquid crystal molecules in a plane parallel to the substrate surface to control the amount of light from a backlight not shown.

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

As shown in Fig. 5, a spacer pedestal 114 is formed on the scanning signal line 36. As shown in Fig. The spacer pedestal 114 is formed by using the same forming material as that of the passivation film 107 (not shown in Fig. 5) formed to cover the scanning signal line 36 on the TFT substrate 100, will be. An alignment film 113 (not shown in FIG. 5) is formed on the spacer pedestal 114. At the portion corresponding to the spacer pedestal 114, the tip end of the columnar spacer 204 formed on the counter substrate is in contact.

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

6, a polarizing plate 120 is formed on the outer side of the TFT substrate 100 and a polarizing plate 220 is formed on the outer side of the opposing substrate 200. As shown in Fig. A liquid crystal 40 is sandwiched between the TFT substrate 100 and the counter substrate 200. That is, the liquid crystal display element 10, which is one example of the first embodiment of the present invention, is characterized in that the liquid crystal 40 is sandwiched between the TFT substrate 100 and the counter substrate 200, And are held by the polarizing plates 120 and 220.

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. A common wiring 39 for supplying a common potential to the common electrode 41 is overlapped with the end of the common electrode 41. The common electrode 41 is formed by being insulated from the scanning signal line 36.

The lower layer of the scanning signal line 36 is formed of the same conductive layer 361 made of ITO as the common electrode 41 and the upper layer of the scanning signal line 36 is formed of a metal film 362 made of the same metal as the common wiring 39 As shown in Fig. The metal film 362 forming the scanning signal line 36 can be formed of, for example, MoW or an Al alloy.

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

The passivation film 107 of the liquid crystal display element 10 is an insulating organic film formed by using the radiation sensitive resin composition of the third embodiment of the present invention to be described later. The spacer pedestal 114 integrally formed thereon as a whole is also 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 may have a planar shape such as a square shape, a rectangular shape, a circular shape, a long circular shape, and an elliptical shape, It is preferable to have a planar shape. 6, the upper end of the spacer pedestal 114 on the side of the liquid crystal 40 is formed to be higher than the upper end of the pixel electrode 42 on the liquid crystal 40 side.

6, the passivation film 107 and the spacer pedestal 114 on the passivation film 107 are distinguished from each other by a broken line. The broken line in FIG. 6 is a convenience formed so that the spacer pedestal 114 becomes clear , The spacer pedestal 114 and the passivation film 107 are integrally formed as one body by using the same material as described above.

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 alignment film, and performing alignment treatment.

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

6, an overcoat film 203 is formed to cover the color filter 202, and columnar spacers 204 (not shown) are formed on the overcoat film 203 so as to protrude from the TFT substrate 100 side, Is formed. The spacer 204 is an example of the spacer 4 on the second substrate 3 in Fig.

The spacer 204 can be formed on the counter substrate 200 by, for example, using a radiation-sensitive resin composition and patterning using a photolithography method. The spacer 204 may have, for example, a truncated cone shape whose tip 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, the spacer 204 can be formed by using the radiation sensitive resin composition of the third embodiment of the present invention, which will be described later, in the same manner as the passivation film 107.

6, the spacer 204 formed on the counter substrate 200 is arranged such that its tip is opposed to the spacer pedestal 114 disposed on the TFT substrate 100. As shown in Fig.

In the counter substrate 200, an alignment film 113 is formed so as to cover the overcoat film 203 and the spacers 204 and to form the same as the TFT substrate.

When an alignment agent for forming the alignment film 113 is applied on the counter substrate 200, the alignment film 113 having a predetermined thickness is formed on the overcoat film 203. However, The alignment film 113 may hardly be formed at the tip of the spacer 204 due to the leveling effect.

The liquid crystal display element 10 having the above structure according to the first embodiment of the present invention has a structure in which the spacer 204 is formed on the counter substrate 200 holding the liquid crystal 40, And a spacer pedestal 114 for receiving the spacer 204 on the passivation film 107 of the substrate 100. Therefore, the liquid crystal display element 10 can uniformly form the thickness of the liquid crystal 40. [

The liquid crystal display element 10 as one example of the first embodiment of the present invention has a structure in which the spacer 204 is formed on the counter substrate 200 and the passivation film A spacer base 114 is formed on the passivation film 107 at a portion where the tip of the spacer 204 is opposed to the spacer base 114 to form a spacer base 114 for receiving the spacer 204, May also be formed. That is, for example, another spacer having the same height can be formed at a position different from the position where the spacer 204 is formed on the TFT substrate 100 of Figs. 5 and 6. Here, the positions at which the other spacers having the same height are formed may be different from the positions where the spacers 204 are formed, for example, above the scanning signal lines 36 in Fig. In the portion of the passivation film 107 opposed to the tip of the other spacer, a spacer pedestal is not formed. In this case, a gap is formed between the tip of the other spacer and the portion of the passivation film 107 opposed thereto.

As described above, in the liquid crystal display element 10 according to the first embodiment of the present invention, the spacer pedestal 114 for receiving the spacer 204 on the TFT substrate 100 is formed, It is possible to realize the structure of the liquid crystal display element 1 of Fig. 1 described above. That is, a plurality of spacers 204 may be formed on the TFT substrate 100 to have the same height, and a step may be formed on the spacer 204. The liquid crystal display element 10, which is an example of the first embodiment of the present invention, can suppress the lowering of the yield in the substrate joining step at the time of its production.

Embodiment 2 Fig.

<Manufacturing Method of Liquid Crystal Display Element>

Next, a method of manufacturing the liquid crystal display element according to the second embodiment of the present invention will be described.

In the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention, the above-described liquid crystal display element according to the first embodiment of the present invention can be manufactured. That is, the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention is a method for manufacturing a liquid crystal display element in which a plurality (two or more) of the first substrate 2 and the second substrate 3, And the spacer base 5 is provided on at least one portion of the insulating film 5 opposite to the tip of the spacer 4 on the insulating substrate 5, And a liquid crystal (not shown) is sandwiched between the first substrate 2 and the second substrate 3 to form a liquid crystal display element.

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

As the second substrate, for example, the counter 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, can be used. That is, a black matrix 201 and a color filter 202 are formed on an insulating substrate such as a glass substrate by using a known method, and the color filter 202 is covered with an overcoat film 203 200) can be used. On the overcoat film 203 of the counter substrate 200, a columnar spacer 204 may be formed so as to protrude toward the TFT substrate 100 by a known method. Therefore, the second substrate having the spacer can be prepared by a known method.

As described above, the method of manufacturing the liquid crystal display element according to the second embodiment of the present invention will be described with reference to Fig. 1 as to a method of collectively forming the insulating film and the spacer pedestal on the first substrate, that is, A method of manufacturing a substrate for a liquid crystal display element having a pedestal will be described in detail.

(Method of manufacturing a substrate having an insulating film and a spacer base)

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

[1] A coating film forming step (hereinafter sometimes referred to as &quot; step [1] &quot;) for forming a coated film of the radiation sensitive resin composition of the third embodiment of the present invention on the first substrate 2, . 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 for the first substrate 2 of the present step.

[2] An exposure step (hereinafter referred to as &quot; step [2] &quot;) for irradiating a coating film of the radiation sensitive resin composition formed in step [1] with radiation using at least one selected from a halftone mask and a gray- ).

[3] A developing step (hereinafter sometimes referred to as "step [3]") for developing a coating film irradiated with radiation in step [2].

[4] A heating step (hereinafter referred to as "step [4]") for heating the developed coating film in step [3].

According to the steps [1] to [4], it is possible to form a pattern of a predetermined shape made of a resin on the first substrate 2 and to form a pattern of a desired composition on the first substrate 2 The insulating film 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 collectively formed integrally.

Hereinafter, the above-mentioned steps [1] to [4] will be described in more detail.

[Process [1]]

In this step, a coating film of the radiation-sensitive resin composition according to the third embodiment of the present invention to be described later is formed on the first substrate 2. The radiation sensitive resin composition of the third embodiment of the present invention to be used will be described in detail later.

In this substrate, the radiation-sensitive resin composition of the third embodiment of the present invention is applied to one side of the substrate, followed by prebaking to evaporate a solvent such as an organic solvent to form a coating film.

As the material of the first substrate 2, for example, a glass substrate such as soda lime glass and non-alkali glass, a silicon substrate, or a substrate such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, Amide, polyamideimide, and polyimide. In addition, these substrates may be subjected to a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, a vacuum A pretreatment such as deposition may be performed. When the TFT substrate 100 of the liquid crystal display element 10, which is an example of the first embodiment of the present invention, is used as the first substrate, the substrate constituting the TFT substrate 100, Mentioned glass substrate, a silicon substrate and a resin substrate can be used.

Examples of the application method of the radiation sensitive resin composition include a spray method, a roll coating method, a rotary coating method (sometimes referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method) A coating method, an ink-jet coating method, and the like can be employed. Of these, a spin coating method or a slit coating method is preferable in that a film having a uniform thickness can be formed.

The above-described prebaking condition is preferably performed at a temperature of 70 to 120 캜, and it is preferable that the prebaking is performed at a temperature of, for example, a hot plate, an oven, or the like, depending on the kinds of components constituting the radiation sensitive resin composition, Depending on the heating apparatus, it can be generally from about 1 minute to about 10 minutes.

[Process [2]]

Next, in this step, a halftone mask made of a semi-transparent film and a gray-tone mask including a semi-transparent area by a slit are selected from the group consisting of the coating film on the first substrate 2 formed in the step [1] At least one of them is used. This makes it possible to appropriately form an insulating film containing a portion having a different film thickness and appropriately 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 the present step is provided with 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.

In the case where the radiation sensitive resin composition to be used has a positive radiation sensitive property, a region where the spacer pedestal 6 is formed on the insulating film 5 shown in Fig. 1, Area. A region where only the insulating film 5 is formed on the first substrate 2 and the spacer pedestal 6 is not formed becomes a half exposure region in which the dose of radiation is controlled. The region where the contact hole 7 of the insulating film 5 is formed becomes a full-exposure region in which radiation is irradiated without controlling the irradiation amount of the radiation.

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

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

The radiation dose in the process [2] is a value measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) of the radiation at a wavelength of 365 nm, M 2 to 10000 J / m 2, and more preferably from 500 J / m 2 to 6000 J / m 2.

In the above-described half-exposure area, a radiation amount that is a smaller value is selected as compared with the irradiation amount in these pool exposure areas, and irradiation with radiation is performed.

[Process [3]]

In this step, unnecessary portions are removed by developing the coating film after irradiation with radiation obtained in the step [2] to form a predetermined insulating film 5 having the spacer pedestal 6 and the contact hole 7 as a cured film ) Are collectively formed. When the coating film of the radiation sensitive resin composition to be used is of the negative type, the non-irradiated portion of the radiation becomes an unnecessary portion. When the coated film of the radiation sensitive resin composition to be used is of the positive type, the irradiated portion of the radiation becomes unnecessary.

As the developer used in the developing step of the process [3], it is preferable to use an alkali developing solution comprising an aqueous solution of an alkali (basic compound). Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia;

Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the like.

Further, a water-soluble organic solvent such as methanol, ethanol and the like or a surfactant may be added to the alkali developing solution in an appropriate amount. The concentration of the alkali in the alkali developing solution may be preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining a suitable developing property. As the developing method, for example, suitable methods such as puddle method, dipping method, oscillating dipping method, and shower method can be used. The developing time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following this developing treatment, for example, the patterning of the insulating film 5 of a desired shape can be performed by conducting water-washing for 30 seconds to 90 seconds and then air-blowing with, for example, compressed air or compressed nitrogen.

[Process [4]]

Then, in this step, the pattern-like coating film 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, and the spacer base 6 and the contact An insulating film 5 having a predetermined shape having holes 7 is formed. The heating temperature is preferably 150 ° C to 350 ° C. By setting the heating temperature to 150 DEG C or higher, it is possible to sufficiently cure the coating film. Further, by setting the temperature at 350 占 폚 or less, it is possible to prevent the thermal deterioration of the first substrate 2 even if the first substrate 2 is formed using the resin substrate. In view of the above, the heating temperature is more preferably 150 ° C to 300 ° C. As the curing time, for example, it is preferably 5 minutes to 30 minutes on a hot plate, and 30 minutes to 180 minutes in an oven.

(Manufacturing Method of Liquid Crystal Display Element)

As described above, in the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention, the second substrate 3 having a plurality of spacers 4, the spacer base 6 and the contact holes 7 are collectively A first substrate 2 having an insulating film 5 formed thereon is prepared to produce a liquid crystal display element.

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

Next, an ultraviolet curable sealing material (not shown in Fig. 1) is applied to a predetermined place on one of the first substrate 2 and the second substrate 3, According to the liquid crystal dropping method, liquid crystal is further dropped onto a predetermined number of places on the alignment film surface, and then the other substrate is bonded so that the liquid crystal alignment film is opposed. 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 material, thereby manufacturing a liquid crystal display panel.

In addition, it is preferable to heat the liquid crystal panel thus manufactured to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cool to room temperature to remove the flow orientation at the time of filling the liquid crystal.

In the above, the liquid crystal is arranged and sandwiched between the first substrate 2 and the second substrate 3 on which the alignment film is formed, and a liquid crystal display panel is manufactured. At this time, as a well-known method for manufacturing the liquid crystal display panel, the first substrate 2 and the second substrate 3 are disposed to face each other with a space (cell gap) interposed therebetween such that the alignment films face each other, It is also possible to use a method in which the peripheral portion is bonded by using a sealing material, the liquid crystal is injected and filled in the space partitioned by the surface of the substrate and the sealing member, and then the injection hole is sealed.

Then, the liquid crystal display element 1 of the first embodiment of the present invention can be obtained by bonding a polarizing plate to the outer surface of the obtained liquid crystal display panel.

3, the liquid crystal display element 1 according to the first embodiment of the present invention includes a first driving circuit 32, a second driving circuit 33, a control circuit 34, The liquid crystal display element 10, which is an example of the first embodiment of the present invention, can be constituted.

Next, the liquid crystal display element 1 of the first embodiment of the present invention and the insulating film of the liquid crystal display element 10 (one example thereof), which is suitably used in the method of manufacturing the liquid crystal display element of the second embodiment of the present invention 5 (passivation film 107) of the radiation sensitive resin composition according to the third embodiment of the present invention.

Embodiment 3:

<Radiation-Resistant Resin Composition>

The radiation sensitive resin composition of the third embodiment of the present invention can be suitably used for forming an 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 the liquid crystal display element of the second embodiment of the present invention which is formed by the method of producing a substrate having an insulating film and a spacer base The insulating film may have a spacer base integrally formed at a desired portion. That is, the radiation-sensitive resin composition according to the third embodiment of the present invention is used to form a coating film on a predetermined substrate, and patterning is carried out using radiation-sensitive properties. Thereafter, as a cured film, The insulating film and the spacer base can be collectively formed integrally.

At this time, the radiation sensitive resin composition of the present embodiment can be provided by selecting any one of the positive and negative radiation sensitive properties.

The radiation sensitive resin composition of the third embodiment of the present invention comprises a polymer comprising a structural unit having a carboxyl group [A] and a radiation sensitive compound [B]. The radiation sensitive resin composition of this embodiment has radiation sensitivity. The radiation sensitive resin composition of the present embodiment may contain a [C] polymerizable unsaturated compound. The radiation sensitive resin composition of the present embodiment may contain other optional components as long as the effect of the present invention is not impaired.

Each component contained in the radiation sensitive resin composition of the third embodiment of the present invention will be described below.

&Lt; Polymer comprising a structural unit having a carboxyl group [A]

(A) a polymer containing a structural unit having a carboxyl group (hereinafter sometimes simply referred to as [A] polymer) contained in the radiation sensitive resin composition of the third embodiment of the present invention,

(A1) a structural unit having a carboxyl group (hereinafter referred to as &quot; structural unit (A1) &quot;),

(A2) a structural unit having a crosslinkable group (hereinafter referred to as &quot; structural unit (A2) &quot;) and

(A3) a structural unit represented by the following formula (1) (hereinafter referred to as "structural unit (A3)"). The polymer [A] may have (A4) a structural unit other than the above-mentioned (A1) to (A3) (hereinafter referred to as "structural unit (A4)").

(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 cycloalkyl group having 3 to 12 carbon atoms, An alkoxy group of 1 to 6 carbon atoms and a phenyl group, and n represents an integer of 1 to 6).

The alkyl group having 1 to 6 carbon atoms represented by R ² in the formula (1) may be any of linear, branched and cyclic. Specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. Examples of the cycloalkyl group having 3 to 12 carbon atoms for R ² in the formula (1) include a cyclohexyl group and the like;

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec- And the period of time when the painting is finished.

The alkyl group having 1 to 6 carbon atoms represented by R ³ in the formula (1) may be any of linear, branched and cyclic. Specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. Examples of the cycloalkyl group having 3 to 12 carbon atoms for R ³ in the formula (1) include a cyclohexyl group and the like;

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec- And the period of time when the painting is finished.

The alkyl group having 1 to 6 carbon atoms represented by R &lt; ⁴ &gt; in the formula (1) may be any of linear, branched and cyclic. Specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. Examples of the cycloalkyl group having 3 to 12 carbon atoms for R ⁴ in the formula (1) include a cyclohexyl group and the like;

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec- And the period of time when the painting is finished.

In the above formula (1), n is preferably an integer of 2 to 6, more 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 oxiranyl group and a (meth) acryloyl group. That is, the structural unit (A2) is a structural unit having at least one kind selected from the group consisting of an oxetanyl group, an oxiranyl group and a (meth) acryloyl group.

The structural unit (A1) is preferably a structural unit derived from (a1) at least one member selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as "compound (a1)");

The structural unit (A2) is preferably a structural unit derived from (a2) a polymerizable unsaturated compound having an oxiranyl group or oxetanyl group (hereinafter referred to as "compound (a2)");

The structural unit (A3) is preferably a structural unit derived from (a3) 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 (a4) a polymerizable unsaturated compound other than the above (a1) to (a3) (hereinafter referred to as "compound (a4)").

(Wherein R ¹ , R ² , R ³ , R ⁴ and n in the formula (a3) have the same meanings as those in the formula (1)).

Examples of the compound (a1) include a monocarboxylic acid, a dicarboxylic acid, and an anhydride of a dicarboxylic acid. Examples of the monocarbonic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2 - methacryloyloxyethylhexahydrophthalic acid and the like;

 Examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid and the like;

 Examples of the anhydride of the dicarboxylic acid include an anhydride of the dicarboxylic acid and the like.

Of these, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, or maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in a developer.

 The compound (a1) may be used alone or in combination of two or more.

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.

Examples of the polymerizable unsaturated compound having an oxiranyl group include oxirane (cyclo) alkyl (meth) acrylate, glycidyl ether compound having a polymerizable unsaturated bond of;

Examples of the polymerizable unsaturated compound having an oxetanyl group include (meta) acrylic acid esters having an oxetanyl group and the like.

Specific examples of the compound (a2)

(Meth) acrylic acid oxiranyl (cyclo) alkyl esters include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyhexyl (meth) acrylate, 3,4-epoxycyclohexyl 4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, and the like;

Examples of the α-alkyl acrylate oxiranyl (cyclo) alkyl esters include glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α- , 7-epoxyheptyl,? -Ethylacrylic acid 3,4-epoxycyclohexyl, and the like;

As the glycidyl ether compound having a polymerizable unsaturated bond, for example,? -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like;

Examples of the (meth) acrylic acid ester having an oxetanyl group include 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) (Meth) acryloyloxymethyl) -2-methyloxetane, 3 - ((meth) acryloyloxyethyl) 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and the like.

Of these, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4 - epoxy tricyclo [5.2.1.0 ^2,6 ] decyl methacrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl acrylate, 3-methacryloyloxymethyl- , 3-methyl-3-methacryloyloxymethyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane are preferred from the viewpoint of polymerizability.

The above-mentioned compounds (a2) may be used alone or in combination of two or more.

[A] The structural unit having a (meth) acryloyloxy group in the polymer containing a structural unit having a carboxyl group is obtained by reacting a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the polymer. 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 (2-2).

In the formula (2-1), R ¹³ is a hydrogen atom or a methyl group. In the formulas (2-1) and (2-2), * represents a bonding site with an oxygen atom.

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

In the above-mentioned reaction of the carboxyl group in the polymer with an unsaturated compound such as a (meth) acrylic acid ester having an epoxy group, an epoxy group is preferably added to a solution of a polymer containing a polymerization inhibitor, preferably in the presence of a suitable catalyst And the mixture is stirred for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium 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 [A] is preferably 10 mol% to 70 mol% of the total components of the polymer [A] , And more preferably 20 mol% to 50 mol%.

When the content of the structural unit having (A2) (meth) acryloyloxy group is less than 10 mol%, the sensitivity of the radiation sensitive resin composition of the present embodiment to radiation tends to be lowered, and the heat resistance Not full yet. In the case where it is contained in an amount of more than 70 mol%, development defects occur at the time of development, and development residue tends to occur.

Examples of the compound (a3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxy Propyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and the like.

The aforementioned compound (a3) may be used singly or in combination of two or more.

Examples of the compound (a4) include (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 (Meth) acrylic acid ester, a vinyl aromatic compound, a conjugated diene compound and other polymerizable unsaturated compounds each having an oxygen-containing 5-membered ring or an oxygen-containing 6-membered ring. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n- Sec-butyl acrylate, t-butyl (meth) acrylate and the like;

Examples of the (meth) acrylic acid cycloalkyl ester include (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, isobornyl (meth) acrylate and the like;

As the (meth) acrylic acid aryl ester, for example, phenyl acrylate and the like;

As the (meth) acrylic acid aralkyl ester, for example, benzyl (meth) acrylate and the like;

As the unsaturated dicarboxylic acid dialkyl ester, for example, diethyl maleate, diethyl fumarate and the like;

(Meta) acrylic acid ester having (meth) acrylic acid tetrahydrofuran-2-yl, (meth) acrylate tetrahydropyran-2-yl, ) 2-methyltetrahydropyran-2-yl acrylate and the like;

As the vinyl aromatic compound, for example, styrene,? -Methylstyrene and the like;

Examples of the conjugated diene compound include 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) exemplified above, n-butyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, styrene, p -Methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.

The compound (a4) may be used alone or in combination of two or more.

The polymer comprising a structural unit having a carboxyl group [A] in the present embodiment is obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing the above-mentioned compounds (a1) to (a4) , Can be synthesized.

The amount of the compound (a1) is preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, and still more preferably 5 mol% to 15 mol%

The amount of the compound (a2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%

The amount of the compound (a3) is preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, further preferably 10 mol% to 30 mol%

The amount of the compound (a4) is preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%

And the like.

The radiation sensitive resin composition of the third embodiment of the present invention contains a polymer containing a structural unit having a carboxyl group [A] obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing the respective compounds in the above ranges, A high resolution can be achieved without deteriorating the good coating property, so that it is possible to give a cured film having a highly balanced balance of characteristics even with a fine pattern, which is preferable.

The weight average molecular weight (hereinafter referred to as &quot; Mw &quot;) of a polymer containing a structural unit having a carboxyl group in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 2000 to 100000 , And more preferably from 5000 to 50000. By using a polymer containing a structural unit having a carboxyl group [M] having a Mw within this range, a high resolution can be achieved without impairing the good coatability, A film can be given.

The polymer containing a structural unit having a carboxyl group [A] in the radiation sensitive resin composition of the third embodiment of the present invention can be obtained by polymerizing a mixture of the above polymerizable unsaturated compounds in an appropriate solvent, preferably Can be produced by polymerization in the presence of a radical polymerization initiator.

Examples of the solvent used in the 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, cyclohexanolacetate, benzyl alcohol and 3-methoxybutanol. These solvents may be used alone or in admixture of two or more.

Examples of the radical polymerization initiator include, but are not limited to, 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 Nate), and the like. These radical polymerization initiators may be used alone or in combination of two or more.

<[B] Radiation-sensitive compounds>

[B] The radiation sensitive compound is to impart the radiation sensitive property to the radiation sensitive composition. The [B] sensitizing radiation compound is a compound which generates an active species which is reactive by exposure to radiation. Here, the radiation includes at least a visible ray, an ultraviolet ray, a far ultraviolet ray, an electron ray (charged particle ray) and an X ray. As the [B] sensitizing radiation compound, (B1) an acid generator, (B2) a polymerization initiator, or a combination thereof is preferable. When the acid generator (B1) is used, any of the positive and negative radiation sensitive compositions may be used with other additives. When a quinone diazide compound is used, a positive radiation-sensitive composition can be used. On the other hand, when the polymerization initiator (B2) is used, a negative radiation-sensitive composition can be used.

((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 a positive radiation sensitive property with respect to, for example, an alkali developing solution by containing (B1) an acid generator.

The acid generator (B1) is not particularly limited as long as it is a compound which generates an acid (for example, a carboxylic acid, a sulfonic acid, or the like) 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, Compounds and the like. Of these, quinone diazide compounds are preferred.

(Quinone diazide compound)

The quinone diazide compound generates carbonic acid by irradiation with radiation. As the quinone diazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as &quot; mother nucleus &quot;) and 1,2-naphthoquinone diazidesulfonic acid halide can be used.

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

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

Examples of the tetrahydroxybenzophenone include 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4' -Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, .

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

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

(P-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1, 2-dihydroxyphenyl) methane, Tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '- [1- [4- [1- [4- hydroxyphenyl] ] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ' 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like.

Examples of the other parent nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- - (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (4-hydroxyphenyl) -1-methylethyl} -1, 4-dihydroxyphenyl} Dihydroxybenzene, and the like.

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

As the 1,2-naphthoquinone diazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable. Examples of the 1,2-naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. have. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferable.

The synthesis of the quinone diazide compound can be carried out by a known condensation reaction. In the condensation reaction, the amount of 1,2-naphthoquinonediamine corresponding to 30% by mole or more and 85% by mole or less, that is, from 30% by mole to 85% by mole, relative to the number of OH groups in the phenolic compound or the alcoholic compound Zidosulfonic acid halide can be used.

Examples of the quinone diazide compound include 1,2-naphthoquinone diazidesulfonic acid amides in which the ester bond of the mother nucleus is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1 , 2-naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

These quinone diazide compounds may be used alone or in combination of two or more. The quinone diazide compound may be used in combination with an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound or a carbonic acid ester compound.

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, and further preferably 20 parts by mass per 100 parts by mass of the polymer [A] More preferable. On the other hand, the upper limit is preferably 80 parts by mass, more preferably 60 parts by mass, further preferably 40 parts by mass. By setting the content of the acid generator (B1) within the above range, the difference in solubility between the irradiated portion of the developer and the unexposed portion of the developer can be increased, and the patterning performance can be improved. Further, the solvent resistance of the insulating film may be made good.

((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 radiation sensitivity characteristic to an alkali developer by including the (B2) polymerization initiator. As the polymerization initiator (B2), a photo radical polymerization initiator may be mentioned. Examples of the photo radical polymerization initiator include O-acyloxime compounds, acetophenone compounds, and imidazole compounds. These compounds may be used alone or in combination of two or more.

(O-acyloxime compound)

Examples of the O-acyloxime compound include 1- [4- (phenylthio) -2- (O-benzoyloxime)] and 1,2-octanedione 1- [4- (phenylthio) -2- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime), 1- [ Ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [ Benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan- Benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4- tetrahydrofuranylbenzoyl) -9H-carbazol- (9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol- (9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- 6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H- ] And the like -1- (O- acetyl oxime).

(Acetophenone compound)

Examples of the acetophenone compound include an? -Amino ketone compound,? -Hydroxy ketone compound and the like.

(? -amino ketone compound)

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one .

(? -hydroxy ketone compound)

Examples of the? -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2- 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl phenyl ketone.

(Nonimidazole compound)

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

The content of the (B2) polymerization initiator in the radiation-sensitive resin composition of the present embodiment may be, for example, 1 part by mass or more and 40 parts by mass or less based on 100 parts by mass of the [A] polymer. By setting the content of the (B2) polymerization initiator within this range, the radiation sensitive resin composition of the present embodiment can form an insulating film having high solvent resistance, hardness and adhesion even at a low exposure dose.

&Lt; [C] Polymerizable unsaturated compound >

The [C] polymerizable unsaturated compound in the radiation sensitive resin composition of the third embodiment of the present invention is an unsaturated compound polymerized by irradiation with radiation in the presence of the above-mentioned [B] radiation sensitive compound. The [C] polymerizable unsaturated compound is not particularly limited, and for example, a monofunctional, bifunctional or trifunctional (meth) acrylic acid ester is preferable because of its excellent polymerizability, The strength is improved.

Examples of the monofunctional (meth) acrylate ester include 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, (2- (meth) acryloyloxyethyl) 2-hydroxypropyl) phthalate, and? -Carboxypolycaprolactone mono (meth) acrylate. M-111, M-114, M-5300 (trade names, manufactured by TOAGOSEI CO., LTD.) Are used as commercial products of these products. For example, Aronix (registered trademark) Produce);

KAYARAD (registered trademark) TC-110S, TC-120S (trade name, manufactured by Nippon Kayaku Co., Ltd.);

Viscoat 158 and 2311 (manufactured by Osaka Organic Chemical Co., Ltd.), and the like.

Examples of the bifunctional (meth) acrylic esters include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate. As commercial products thereof, for example, ARONIX (registered trademark) M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) HDDA, HX-220, R-604 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Viscot 260, Copper 312 and Copper 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) NDA (manufactured by Kyoeisha Kagaku Co., Ltd.) and the like.

Examples of the trifunctional or more (meth) acrylic acid esters include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate;

A mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate;

(Meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, succinic acid-modified dipentaerythritol penta (metha) acrylate, ) Acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a mixture of isocyanuric acid EO-modified diacrylate and isocyanuric acid EO-modified triacrylate;

A compound having two or more isocyanate groups and having a linear alkylene group and an alicyclic structure and a compound having at least one hydroxyl group in the molecule and having three, four or five (meth) acryloyloxy groups Polyfunctional urethane acrylate compounds and the like.

Examples of commercial products of the above-mentioned three or more functional (meth) acrylic acid esters include ARONIX (registered trademark) M-309, M-400, M-405, M- KAYARAD (registered trademark) TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60 (manufactured by Toagosei Co., Ltd.) , DPCA-120, DPEA-12 (manufactured by NIPPON KAYAKU CO., LTD.), Viscot 295, 300, Dong 360, Copper GPT, Copper 3PA, Copper 400 New Frontier TM R-1150 (manufactured by Daiichi Kyoei Co., Ltd.), KAYARAD (registered trademark) DPHA-1150 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) or a polyfunctional urethane acrylate- 40H (manufactured by Nippon Kayaku Co., Ltd.).

Of these, particularly preferred are ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Dipentaerythritol hexaacrylate;

A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;

A mixture of tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate;

A commercially available product containing ethylene oxide-modified dipentaerythritol hexaacrylate, polyfunctional urethane acrylate-based compound, succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylate is preferable.

The above-mentioned [C] polymerizable unsaturated compounds may be used singly or in combination of two or more kinds.

The proportion 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 relative to 100 parts by mass of the polymer [A] And preferably 50 parts by mass to 200 parts by mass. By setting the ratio of the [C] polymerizable unsaturated compound within the above range, it is possible to form a cured film with a high resolution without causing a problem of development residue, which is preferable.

(Other arbitrary components)

The radiation sensitive resin composition according to the third embodiment of the present invention contains a structural unit having a carboxyl group in addition to or in addition to the polymer comprising a structural unit having a carboxyl group and the [B] radiation-sensitive compound , The polymer [B], the radiation-sensitive compound [C] and the polymerizable unsaturated compound [C] may contain other arbitrary components as necessary insofar as the effect of the present invention is not impaired. Examples of other optional components that can be used herein include [D] an adhesion aid, [E] a surfactant, and [F] a polymerization inhibitor. The other arbitrary components may be used by mixing two or more kinds. Each optional component will be described below.

[D] Adhesive preparation

The [D] adhesion aid can be used to further improve adhesion between the cured film to be formed and the substrate. As such a [D] adhesion aid, there can be used the same compounds as the above-mentioned compound (a3), but also trimethoxysilylbenzoic acid, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl Trimethoxysilane and the like can be used. The proportion of the [D] adhesion aid used in the radiation sensitive resin composition of the present embodiment is preferably 20 parts by mass or less, more preferably 1 part by mass to 10 parts by mass, relative to 100 parts by mass of the polymer [A] Mass part. [D] When the content ratio of the adhesive aid is within the above range, adhesion between the formed cured film and the substrate is effectively improved.

[E] Surfactant

Examples of the [E] surfactant include a fluorine-based surfactant and a silicone-based surfactant. The proportion 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 to 0.6 part by mass, per 100 parts by mass of the polymer [A] Mass part.

[F] polymerization inhibitor

The [F] polymerization inhibitor is a component that inhibits cleavage of molecules of the polymer [A] by capturing radicals generated by exposure or heating, or decomposing peroxides produced by oxidation. Since the radiation-sensitive resin composition of the present embodiment contains the [F] polymerization inhibitor, the deterioration in the deterioration of the polymer molecules in the cured film to be formed is suppressed. In the resulting cured film, for example, .

Examples of such a [F] polymerization inhibitor include a hindered phenol compound, a hindered amine compound, an alkyl phosphite compound, and a thioether compound. Of these, hindered phenol compounds may be preferably used.

Examples of the hindered phenol compound include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- Di (tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- Tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5- Benzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert- butyl-4-hydroxyphenylpropionamide)], 3,3 ' A ', a' - (mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o -Cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert- 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- (2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol.

Examples of commercially available products thereof include ADKSTAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO- Sumitomo (registered trademark) GM, copper GS, copper MDP-S, copper BBM-S, copper WX-R, copper GA-80 (manufactured by ADEKA) IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565 , IRGAMOD295 (manufactured by BASF), YOSHINOX (registered trademark) BHT, copper BB, copper 2246G, copper 425, copper 250, copper 930, copper SS, copper TT, copper 917, (Manufactured by API Corporation).

As the [F] polymerization inhibitor in the present embodiment, the above-mentioned middle pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris- (3 , 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate is preferably used.

[F] The content of the polymerization inhibitor is preferably 10 parts by mass or less, more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the polymer [A]. By setting the content in this range, it is possible to effectively suppress the deterioration in cleanness of the cured film without impairing the effects of the present invention.

(Preparation of radiation-sensitive resin composition)

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

The radiation sensitive resin composition according to the third embodiment of the present invention contains a structural unit having a carboxyl group in addition to or in addition to the polymer comprising a structural unit having a carboxyl group and the [B] radiation-sensitive compound , [E] a surfactant, and the like, in addition to the [B] radiation-sensitive compound and the [C] polymerizable unsaturated compound. At this time, an organic solvent may be used for preparing the liquid radiation-sensitive resin composition. The organic solvent may be used alone or in combination of two or more.

Examples of the function of the organic solvent include adjusting the viscosity and the like of the radiation-sensitive resin composition to improve the applicability to a substrate or the like, as well as improving operability and moldability. The viscosity of the radiation-sensitive resin composition realized by incorporating an organic solvent or the like is preferably 0.1 mPa · s to 50000 mPa · s (25 ° C.), more preferably 0.5 mPa · s to 10000 mPa · s s (25 캜).

Examples of the organic solvent usable in the radiation sensitive resin composition of the third embodiment of the present invention include those which dissolve or disperse other contained components and do not react with other contained components.

For example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol;

Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanol;

Esters such as ethyl acetate, butyl acetate, ethyl lactate,? -Butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and methyl-3-methoxypropionate;

Ethers such as polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether;

Aromatic hydrocarbons such as benzene, toluene and xylene;

And amides such as dimethylformamide, dimethylacetamide and 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.

[Example]

Hereinafter, embodiments of the present invention will be described in detail on the basis of examples, but the present invention is not limited to these examples.

[Synthesis Example 1]

<Synthesis (A) of a polymer containing a structural unit having a carboxyl group ([A] polymer)

A cooling tube, and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were added, and then 55 parts by mass of methacrylic acid, benzyl methacrylate 45 And 2 parts by mass of? -Methylstyrene dimer as a molecular weight modifier were added and the temperature of the solution was raised to 80 占 폚 while being gently stirred. The temperature of the solution was maintained for 4 hours and then raised to 100 占 폚, Was kept for 1 hour and polymerized to obtain a solution containing the copolymer. Subsequently, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 part by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 DEG C for 30 minutes in an air atmosphere. Then, glycidyl methacrylate (Solid content concentration = 35.0% by mass) was obtained by adding 74 parts by mass of the polymer (A-1) and reacting at 90 캜 for 10 hours. The polymer (A-1) had a weight average molecular weight Mw of 9000.

[Synthesis Example 2]

<Synthesis (A) of a polymer containing a structural unit having a carboxyl group ([A] polymer)

A cooling tube, and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, and further, 18 parts by mass of methacrylic acid, [5.2.1.0 ^2,6 ] decan-8-yl, 5 parts of styrene, 20 parts of 3-acryloxypropyltrimethoxysilane and 32 parts of glycidyl methacrylate were charged and replaced with nitrogen, , The temperature of the solution was raised to 80 캜. This temperature was maintained for 5 hours and polymerized to obtain a solution containing 28.8% by mass of the polymer (A-2). The Mw of this polymer (A-2) was 12,000.

[Example 1]

<Preparation of positive-tone radiation-sensitive resin composition>

100 parts by mass of the polymer [A] containing the polymer (A-1) obtained in Synthesis Example 1 in terms of solid content as the polymer, 10 parts by mass of the following (B-1) as the polymerization initiator as the radiation- , 100 parts by mass of the following (C-1) as the [C] polymerizable unsaturated compound were mixed and propylene glycol monomethyl ether acetate was added as a solvent so that the solid concentration became 30 mass% Followed by filtration with a forer filter to prepare the radiation-sensitive resin composition of Example 1.

[Example 2]

&Lt; Preparation of positive-tone radiation-sensitive resin composition >

100 parts by mass of the solution containing the polymer (A-2) obtained in Synthesis Example 2 as the polymer [A] in an amount of 100 parts by mass in terms of solid content, [B] And the resultant was added with propylene glycol monomethyl ether acetate as a solvent so as to have a solid content concentration of 30 mass% and filtered through a Millipore filter having a pore size of 0.5 탆 to prepare a radiation-sensitive resin composition of Example 2.

Details of each component used in Example 1 and Example 2 are shown below.

[B] Radiation-sensitive compound

B-1: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01,

B-2: Synthesis of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediamine 5-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]

&Lt; Production and Evaluation of Liquid Crystal Display Device >

The liquid crystal display element of this embodiment is an active matrix type FFS mode liquid crystal display element. The liquid crystal display element of this embodiment has the same structure as the liquid crystal display element 10 which is one example of the first embodiment of the present invention described with reference to Figs.

The liquid crystal display element of this embodiment is manufactured by manufacturing a TFT substrate on which a TFT and an insulating film are formed, preparing an opposing substrate on which a color filter and a spacer are formed, and then sealing the liquid crystal between the substrates according to a liquid drop- did.

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

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

Next, a liquid crystal aligning agent A-1 described in Example 6 of the International Publication WO / 2009/25386 pamphlet was coated on a TFT substrate by a spinner as an aligning agent containing a radiation sensitive polymer having a photo aligning group did. Subsequently, the substrate was prebaked on a hot plate at 80 DEG C for 1 minute, and then heated at 180 DEG C for 1 hour in an oven where the inside was replaced with nitrogen to form a coating film of an alignment agent with a thickness of 80 nm. Subsequently, polarizing ultraviolet rays 200 J / m &lt; 2 &gt; containing a bright line of 313 nm were irradiated onto the surface of the coating film in a direction of 40 DEG with respect to the direction perpendicular to the substrate surface using an Hg-Xe lamp and a Gantay prism, Was fabricated.

Next, a counter substrate was manufactured according to a known method and Patent Document 1. On the opposed substrate, a spacer was formed on the overcoat film covering the color filter and the black matrix. The spacer had a tapered shape and had a height of about 4.2 mu m. The alignment film of the counter substrate was formed in the same manner as the TFT substrate described above.

Next, the manufactured TFT substrate and the counter substrate were bonded to each other to seal the liquid crystal. That is, an annular sealing material was applied to the outer peripheral portion of the display region of the counter substrate, and liquid crystal was dropped to the region surrounded by the sealing material, and then the liquid crystal was bonded to the TFT substrate. The liquid crystal was a nematic liquid crystal composition having a dielectric anisotropy DELTA epsilon and a refractive index anisotropy DELTA n of 0.075. The thickness (cell gap) of the liquid crystal was 4.2 mu m which is almost the same as the height of the spacer.

Next, bonding was performed using a pair of polarizing plates. Then, a first driving circuit, a second driving circuit, a control circuit, a backlight and the like were connected and modulated to manufacture a liquid crystal display element.

Next, a lighting test was conducted using the liquid crystal display device manufactured. As a result, it was found that the manufactured liquid crystal display device is capable of uniform black display with low brightness and no display unevenness. Further, by using the manufactured liquid crystal display element, the display area was temporarily subjected to external pressure, and the state of disturbance of the display was visually observed. As a result, it was found that although the disturbance of the display due to the disturbance of the liquid crystal alignment occurred immediately after the application of the pressure, the degree was slight. Further, when the application of the external pressure is stopped, the disturbance of the display is quickly resolved, and the display returns to the original display state before the application of the pressing force.

Next, using the radiation sensitive composition prepared in Example 2, a liquid crystal display device was produced in the same manner as in the case of using the radiation sensitive composition prepared in Example 1 described above, and the lighting test was conducted. As a result, as in the case of using the radiation sensitive composition prepared in the above-mentioned Example 1, the liquid crystal display device manufactured using the radiation sensitive composition prepared in Example 2 had a low luminance and no display unevenness It was found that uniform black display was possible. Further, the liquid crystal display element was used to temporarily apply external pressure to the display area, and the state of disturbance of the display was visually observed. As a result, as in the case of using the radiation sensitive composition prepared in the above-mentioned Example 1, display irregularity due to disturbance of the liquid crystal alignment occurred immediately after the application of pressure, but it was found to be slight I could. Further, when the application of the external pressure is stopped, the disturbance of the display is quickly resolved, and the display returns to the original display state before the application of the pressing force.

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 a liquid crystal that is 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 smart phone or a large-sized liquid crystal TV which is strongly required to display in an excellent image quality.

1, 10, 1001: liquid crystal display element
2, 1002: a first substrate
3, 1003: second substrate
4, 204: Spacer
5, 1005: insulating film
6, 114: spacer base
7, 1007: contact hole
32: first driving circuit
33: second driving circuit
34: Control circuit
35: backlight
36: scanning signal line
37: Video signal line
38: Display area
39:
40: liquid crystal
41: common electrode
42:
43: TFT
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: polarizer
200: opposing substrate
201: Black Matrix
202: Color filter
203: overcoat film
361: conductive layer
362: metal film
1004: Main spacer
1014: sub spacer

Claims (14)

And a plurality of spacers disposed on the second substrate of the first substrate and the second substrate arranged to face each other,
A spacer having a spacer base on at least one of a portion of the first substrate facing the tip of the spacer on the insulating film,
And a liquid crystal interposed between the first substrate and the second substrate, the method comprising:
(1) a coating film forming step of forming a coating film of the 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 the insulating film having the spacer pedestal is collectively formed on the first substrate. The method according to claim 1,
In the exposure step (2), at least one selected from the halftone mask and the gray-tone mask is used to irradiate the coating, and the coating film of the radiation-sensitive resin composition is coated with at least two portions different in irradiation dose of the radiation Forming,
(2) one of the two parts of the exposure step forms the insulating film and the spacer base disposed thereon by the developing step (3) and the heating step (4), and the other part And forming the insulating film. 3. The method according to claim 1 or 2,
The radiation-sensitive resin composition may contain,
[A] a polymer comprising a structural unit having a carboxyl group,
[B] Radiation-sensitive compound
Wherein the liquid crystal display element is a liquid crystal display element. The method of claim 3,
[A] A process for producing a liquid crystal display element, wherein the polymer comprising a structural unit having a carboxyl group further has a crosslinkable group. The method of claim 4, wherein
Wherein the crosslinkable group is at least one selected from the group consisting of an oxetanyl group, an oxiranyl group and a (meth) acryloyl group. The method of claim 3,
A process for producing a liquid crystal display element, wherein the polymer comprising the structural unit having a carboxyl group [A] is a polymer having a structural unit represented by the following formula (1)

(Wherein 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 cycloalkyl group having 3 to 12 carbon atoms, An alkoxy group having 1 to 6 carbon atoms;
and n represents an integer of 1 to 6). And a plurality of spacers disposed on the second substrate of the first substrate and the second substrate facing each other and having an insulating film on the first substrate and at least one portion of the portion of the insulating film facing the tip of the spacer on the insulating film And a liquid crystal display element in which a liquid crystal is sandwiched between the first substrate and the second substrate and which has a spacer base and the spacer base are arranged in parallel to each other by using at least one selected from a halftone mask and a gray- As the radiation sensitive resin composition used for collective formation by irradiation,
[A] a polymer comprising a structural unit having a carboxyl group,
[B] Radiation-sensitive compound
Wherein the radiation-sensitive resin composition is a thermosetting resin composition. 8. The method of claim 7,
[A] The radiation-sensitive resin composition according to any one of [1] to [4], wherein the polymer comprising a structural unit having a carboxyl group further has a crosslinkable group. 9. The method of claim 8,
Wherein the crosslinkable group is at least one member selected from the group consisting of an oxetanyl group, an oxiranyl group and a (meth) acryloyl group. 10. The method according to any one of claims 7 to 9,
The radiation-sensitive resin composition according to any one of [1] to [5], wherein the polymer comprising a structural unit having a carboxyl group [A] is a polymer having a structural unit represented by the following formula

(Wherein 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 cycloalkyl group having 3 to 12 carbon atoms, An alkoxy group having 1 to 6 carbon atoms;
and n represents an integer of 1 to 6). 10. The method according to any one of claims 7 to 9,
[B] The radiation-sensitive resin composition according to any one of the above items, wherein the radiation-sensitive compound is an acid generator, a polymerization initiator, or a combination thereof. And a plurality of spacers disposed on the second substrate of the first substrate and the second substrate arranged to face each other,
A spacer having a spacer base on at least one portion of the insulating film on the insulating substrate opposite to the tip of the spacer,
And a liquid crystal interposed between the first substrate and the second substrate,
Wherein the insulating film on the first substrate and the spacer base 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 the 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,
(4) A heating process for heating the developed coating film. 13. The method of claim 12,
The radiation-sensitive resin composition may contain,
[A] a polymer comprising a structural unit having a carboxyl group,
[B] Radiation-sensitive compound
Wherein the liquid crystal display element is a liquid crystal display element. And a plurality of spacers disposed on the second substrate of the first substrate and the second substrate facing each other and having an insulating film on the first substrate and at least one portion of the portion of the insulating film facing the tip of the spacer on the insulating film And a liquid crystal interposed between the first substrate and the second substrate.

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