WO2015076219A1 - Liquid crystal display element and radiation-sensitive resin composition - Google Patents

Abstract

Provided is a liquid crystal display element which is suppressed in decrease of display quality and is able to be produced easily. This liquid crystal display element (1) comprises: a liquid crystal layer (4); a first substrate (2) and a second substrate (3) which are arranged so as to face each other and to sandwich the liquid crystal layer (4); a pixel electrode (5) which is provided on the liquid crystal layer (4)-side surface of the first substrate (2); and a counter electrode (6) that is provided on the second substrate (3) so as to face the pixel electrode (5). The liquid crystal layer (4)-side surface of the pixel electrode (5) has a recessed and projected structure (10) having a height difference within the range of 0.1-2.0 μm. The recessed and projected structure (10) is formed by arranging a pattern (11) between the pixel electrode (5) and the first substrate (2), said pattern being formed of a resin. The pattern (11) is formed using a radiation-sensitive resin composition that contains (A) an alkali-soluble resin and (B) a sensitizing agent.

Description

Liquid crystal display element and radiation sensitive resin composition

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

Liquid crystal display elements include a reflective type and a transmissive type using a backlight.

For example, when the liquid crystal display element is a transmissive type, a transparent first substrate disposed on the viewer side and a transparent second substrate disposed on the opposite side of the viewer so as to face the first substrate. The liquid crystal layer is sandwiched between the first substrate and the second substrate. The liquid crystal layer can be formed using, for example, nematic liquid crystal (hereinafter also referred to as nematic liquid crystal). The liquid crystal display element has an advantage that it can be made thinner and lighter than a conventional CRT display device.

Liquid crystal display elements are classified into several modes (types) based on the initial alignment state of the liquid crystal in the liquid crystal layer and the operation when an electric field is applied. For example, in addition to a liquid crystal display element known as a TN (Twisted Nematic) type or STN (Super Twisted Nematic) type, the liquid crystal of the liquid crystal layer in an initial alignment where no electric field is applied is perpendicular or substantially perpendicular to the substrate surface. There is a liquid crystal display element having a vertical alignment structure. A liquid crystal display element in which liquid crystal is vertically aligned is referred to as a VA (Vertical Alignment) type liquid crystal display element (see, for example, Patent Document 1, Patent Document 2, and Non-Patent Document 1).

In a VA liquid crystal display element, a liquid crystal having a negative dielectric anisotropy (Δε) is used for forming a liquid crystal layer. On each of the first and second substrates, a pair of polarizing plates are arranged so as to normally form a crossed Nicol with a liquid crystal layer interposed therebetween. Electrodes are provided on the inner surfaces of the first and second substrates on the liquid crystal layer side. This electrode can be formed using a transparent conductive material such as ITO (Indium Tin Oxide).

When a voltage is applied to the liquid crystal layer using the electrodes of the VA type liquid crystal display element, the alignment of the liquid crystal in the liquid crystal layer changes and is perpendicular to the electric field in which the liquid crystal is formed, that is, the alignment direction of the liquid crystal. Tries to be parallel to the substrate. Thereby, in the portion where voltage is applied, light transmission determined by the product (Δn · d) of the refractive index anisotropy (Δn) of the liquid crystal and the thickness (d) of the liquid crystal layer, compared to the initial alignment state of the liquid crystal. The characteristic changes. In the VA liquid crystal display element, a desired display is performed by utilizing the property that the light transmission characteristic changes in the voltage application portion.

VA type liquid crystal display elements are superior in response characteristics and can realize high contrast display as compared with TN type liquid crystal display elements and STN type liquid crystal display elements. VA-type liquid crystal display elements are actively used for, for example, display devices for liquid crystal televisions and portable information devices, and so-called in-vehicle devices such as instrument panels for vehicles such as automobiles.

In such a VA-type liquid crystal display element, as described above, the liquid crystal in the liquid crystal layer in the initial alignment is vertically or substantially perpendicular to the substrate surface. However, it may not be preferable for the liquid crystal to be completely vertically aligned in the initial alignment state where no voltage is applied.

That is, in the VA liquid crystal display element, when a voltage is applied between electrodes sandwiching the liquid crystal layer, a voltage in a direction completely perpendicular to the substrate surface can be applied. At that time, if the liquid crystal in the initial alignment state is perfectly perpendicular to the substrate, the direction in which the liquid crystal is tilted cannot be defined when a voltage is applied. As a result, in the VA liquid crystal display element, the orientation of the liquid crystal when voltage is applied is not uniform, and the display quality is deteriorated. Therefore, in the VA liquid crystal display element, the electrode shape is devised by some method to define the direction in which the vertically aligned liquid crystal is tilted by voltage application, and the tilt angle pre-tilt angle is given to the liquid crystal in the liquid crystal layer. There is a need to.

For example, in a VA liquid crystal display element, there is a method of providing a slit such as a notch or an opening in an electrode as a method for defining the direction in which the liquid crystal is tilted (see, for example, Patent Document 3). However, in the case of an electrode provided with a slit, a voltage cannot be applied to the liquid crystal layer in the slit portion, and the liquid crystal in the liquid crystal layer in the vicinity of the electrode hardly changes its orientation. As a result, the transmittance at the time of voltage application is reduced in the slit portion of the electrode, which may reduce the display quality of the liquid crystal display element.

JP 2011-232736 A JP 2011-085738 A JP 2010-097226 A

Masashi Miyakawa, 5 others, “High Transmissivity VA-LCD for the 4K x 2K display with 3D shape pixel electrode (High Transmission VA-LCD Width 3D Shielded2K”) ”SID 2013 Digest, pp. 107-110

Therefore, a technique for eliminating the need for electrode slits in a VA liquid crystal display element has been studied.

For example, as described in Patent Document 1 and Non-Patent Document 1, a concavo-convex structure is formed on at least one liquid crystal layer side surface of the electrode on the first substrate and the electrode on the second substrate that sandwich the liquid crystal layer. A technique for providing a VA liquid crystal display element has been proposed.

In the liquid crystal display element described in Patent Document 1 and Non-Patent Document 1 described above having an uneven structure on the electrode surface, a voltage is applied between the electrode on the first substrate and the electrode on the second substrate. When applied, electric field distortion occurs in the liquid crystal layer, and the tilt alignment direction of the liquid crystal when a voltage is applied can be regulated to a desired constant direction. And the liquid crystal display element does not need to provide a slit in an electrode, and can suppress the fall of the transmittance | permeability at the time of voltage application, and a fall of display quality by extension.

However, in the liquid crystal display elements described in Patent Document 1 and Non-Patent Document 1, it is necessary to provide a uniform concavo-convex structure with a desired size on the electrode surface on the substrate. It was said.

For example, in the liquid crystal display element of Non-Patent Document 1, a thin film made of resin is formed on a substrate, and this is dry-etched to form a stripe-shaped resin pattern. Then, an ITO material layer is formed on the resin pattern to form an electrode, and as a result, a striped uneven structure is formed on the electrode surface.

At this time, the dry etching process is particularly troublesome work, such as requiring a large-scale apparatus. In the liquid crystal display element described in Patent Literature 1, a resin thin film having a thickness of about 2 μm on a substrate is patterned to form a stripe-shaped resin pattern uniformly formed in a desired size. Desired. Therefore, although very complicated, a dry etching process capable of meeting such a demand has been adopted.

Therefore, in a liquid crystal display element, in particular, a VA liquid crystal display element, there is a demand for a technique for suppressing a deterioration in display quality by forming an uneven structure on the electrode surface by a simple operation. That is, there is a demand for a liquid crystal display element that can suppress the deterioration of display quality and can be easily manufactured.

The present invention has been made in view of the above points. That is, an object of the present invention is to provide a liquid crystal display element that can be easily manufactured while suppressing deterioration in display quality.

Another object of the present invention is to provide a radiation-sensitive resin composition used in the production of a liquid crystal display element that suppresses deterioration in display quality.

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 liquid crystal layer, first and second substrates disposed so as to sandwich the liquid crystal layer, a pixel electrode provided on the liquid crystal layer side of the first substrate, A counter electrode provided on the second substrate facing the pixel electrode, and having a height difference of 0.1 μm to 2.0 μm on at least one liquid crystal layer side surface of the pixel electrode and the counter electrode A liquid crystal display element having a concavo-convex structure,
The concavo-convex structure is formed by arranging a pattern formed using a radiation-sensitive resin composition between at least one of the pixel electrode and the first substrate and between the counter electrode and the second substrate. The present invention relates to a liquid crystal display element.

In the first aspect of the present invention, the liquid crystal layer is preferably vertically aligned with at least one of the first and second substrates in a state where no voltage is applied between the pixel electrode and the counter electrode.

In the first aspect of the present invention, the pattern is preferably a stripe pattern.

In the first aspect of the present invention, the radiation sensitive resin composition comprises:
[A] It is preferable to contain an alkali-soluble resin and [B] a photosensitizer.

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

In the first aspect of the present invention, the concavo-convex structure has a pixel electrode formed by depositing ITO after forming a pattern on the first substrate using a radiation-sensitive resin composition, and a liquid crystal layer of the pixel electrode. It is preferable that it is provided on the side surface.

The second aspect of the present invention relates to a radiation-sensitive resin composition that is used for forming an uneven structure of the liquid crystal display element of the first aspect of the present invention.

According to the first aspect of the present invention, it is possible to provide a liquid crystal display element that can be easily manufactured while suppressing a reduction in display quality.

According to the second aspect of the present invention, there is provided a radiation-sensitive resin composition used for the production of a liquid crystal display element in which the deterioration of display quality is suppressed.

It is sectional drawing which shows typically the pixel structure of the liquid crystal display element of embodiment of this invention. It is a perspective view which illustrates typically the pattern arrange | positioned on the 1st board | substrate of the liquid crystal display element of embodiment of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

<Liquid crystal display element>
FIG. 1 is a cross-sectional view schematically showing a pixel structure of a liquid crystal display element according to an embodiment of the present invention.

The liquid crystal display element 1 according to the embodiment of the present invention includes a liquid crystal layer 4, first and second substrates 2 and 3 that are disposed so as to sandwich the liquid crystal layer 4, and liquid crystal of the first substrate 2. The pixel electrode 5 provided on the layer 4 side and the counter electrode 6 provided on the second substrate so as to face the pixel electrode 5 are provided.

Then, the liquid crystal display element 1 of the present embodiment has unevenness on the surface of the pixel electrode 5 on the liquid crystal layer 4 side, that is, the unevenness in which the distance between the concave and convex surfaces is in the range of 0.1 μm to 2.0 μm. It has structure 10.

The concavo-convex structure 10 of the liquid crystal display element 1 is formed by disposing a pattern 11 made of a resin between the pixel electrode 5 and the first substrate 2.

FIG. 2 is a perspective view schematically illustrating a pattern arranged on the first substrate of the liquid crystal display element of the embodiment of the invention.

In the liquid crystal display element 1 of the present embodiment, the pattern 11 has a stripe structure in which a plurality of strip-shaped resin materials are arranged on the first substrate 2 at regular intervals.
The pattern 11 is formed by a simple method using the radiation-sensitive resin composition of the embodiment of the present invention to be described in detail later.

The liquid crystal 7 of the liquid crystal layer 4 is in a state where a voltage for driving the liquid crystal 7 is not applied between the pixel electrode 5 and the counter electrode 6 (hereinafter sometimes referred to as OFF), and the first substrate 2 and the first substrate 2. 2 is vertically aligned with the second substrate 3. Then, the liquid crystal display element 1 changes the orientation of the liquid crystal 7 in a state where a voltage for driving the liquid crystal 7 is applied between the pixel electrode 5 and the counter electrode 6 (hereinafter sometimes referred to as ON). The first substrate 2 and the second substrate 3 are aligned in parallel. That is, the liquid crystal display element 1 of the embodiment of the present invention constitutes a VA liquid crystal display element.

Hereinafter, the configuration of the liquid crystal display element 1 of the present embodiment will be described in more detail.

The distance between the first substrate 2 and the second substrate 3 is set to 2 μm to 20 μm, and these are fixed to each other by a sealing material (not shown) provided in the peripheral portion.

Examples of the material constituting the first substrate 2 and the second substrate 3 include glass such as soda lime glass and non-alkali glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, Examples thereof include polyamideimide and polyimide. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

The pixel electrode 5 on the first substrate 2 and the counter electrode 6 on the second substrate 3 are similarly formed using a conductive member. Examples of the conductive member that constitutes the pixel electrode 5 and the counter electrode 6 include transparent conductive materials such as ITO, zinc oxide-based AZO (Aluminum doped Zinc Oxide), and GZO (Gallium doped Zinc Oxide).

As described above, the liquid crystal display element 1 is made of resin between the pixel electrode 5 and the first substrate 2 so that the uneven structure 10 is formed on the surface of the pixel electrode 5 on the liquid crystal layer 4 side. The pattern 11 is arranged.

When the liquid crystal display element 1 is turned on, it generates an electric field in a direction perpendicular to the substrate surface between the electrodes and generates an electric field distortion in the liquid crystal layer 4. The electric field distortion causes the electric field formed between the electrodes to contain a component in a direction parallel to the substrate surface. As a result, the liquid crystal display element 1 can regulate the tilt alignment direction of the liquid crystal 7 to a desired constant direction. At this time, the electric field distortion of the liquid crystal layer 4 when the liquid crystal display element 1 is ON can be formed by the concavo-convex structure 10 on the surface of the pixel electrode 5 on the liquid crystal layer 4 side. Therefore, in the liquid crystal display element 1, the uneven structure 10 on the surface of the pixel electrode 5 is an important component.

In the liquid crystal display element 1 of the present embodiment, the uneven structure 10 on the surface of the pixel electrode 5 is formed by disposing the pattern 11 made of resin between the pixel electrode 5 and the first substrate 2 as described above. Is done. That is, in the liquid crystal display element 1 of the present embodiment, the uneven structure 10 on the surface of the pixel electrode 5 is derived from the shape of the pattern 11.

In the liquid crystal display element 1, the pattern 11 has a striped structure in which a plurality of strip-shaped resin materials are arranged on the first substrate 2 at regular intervals, as shown in FIG. And the resin material which comprises the pattern 11 has a strip shape whose cross section becomes a rectangle or a square. Since the resin material of the pattern 11 has such a structure, the uneven structure 10 on the surface of the pixel electrode 5 on the liquid crystal layer 4 side has, for example, the structure shown in FIG. That is, the concavo-convex structure 10 on the surface of the pixel electrode 5 has a concave surface and a convex surface alternately along a direction parallel to the surface of the first substrate 2, and a step portion between them is formed on the surface of the first substrate 2. It becomes a vertical vertical plane.

The liquid crystal display element 1 can generate a desired electric field distortion in the liquid crystal layer 4 at the time of ON by the concavo-convex structure 10 of the pixel electrode 5 having a structure in which the concave surface and the convex surface are connected by a vertical surface. At this time, the distance between the concave and convex surfaces of the concavo-convex structure 10, that is, the height difference in the concavo-convex structure 10, is preferably in the range of 0.1 μm to 2.0 μm as described above. The width of the concave surface is preferably in the range of 0.1 μm to 2.0 μm, and the width of the convex surface is also preferably in the range of 0.1 μm to 2.0 μm.

Since the pixel electrode 5 has such a concavo-convex structure 10 on the surface on the liquid crystal layer 4 side, the liquid crystal display element 1 generates an electric field distortion at the time of ON, and is moderate between the pixel electrode 5 and the counter electrode 6. An oblique electric field can be generated.

In the liquid crystal display element 1, it is preferable to provide an alignment film (not shown) on the opposing surfaces of the first substrate 2 and the second substrate 3, respectively. The alignment film can be provided on the surface of the first substrate 2 and the second substrate 3 in contact with the liquid crystal layer 4, for example, on the surface of the pixel electrode 5 and the counter electrode 6 on the liquid crystal layer 4 side. The alignment film can be a vertical alignment film formed using a polymer material such as polyimide or polysiloxane. The vertical alignment film aligns the long axis direction of the liquid crystal 7 of the liquid crystal layer 4 perpendicular to the substrate surface. Such an alignment film can be formed by using a liquid alignment agent prepared containing polyimide, polysiloxane, or a precursor thereof, forming the coating film, and then drying by heating.

In the liquid crystal display element 1, the liquid crystal layer 4 can be formed using, for example, nematic liquid crystal. In the liquid crystal layer 4, the liquid crystal 7 has a rotationally symmetric shape with the major axis and the minor axis as the central axes, respectively, and negative dielectric anisotropy (the dielectric constant in the major axis direction is smaller than that in the minor axis direction). Property).

FIG. 1 also illustrates the formation of the pretilt angle of the liquid crystal 7a in the vicinity of the pixel electrode 5 in the liquid crystal display element 1 of the present embodiment.

In the liquid crystal display element 1 of the present embodiment, the liquid crystal 7a in the vicinity of the interface with the pixel electrode 5 on which the alignment film (not shown) is formed is arranged so that the major axis direction is substantially perpendicular to the substrate surface by the restriction from the alignment film. While being oriented, it can be held in a slightly inclined state from the vertical direction. That is, in the vicinity of the interface between the liquid crystal layer 4 and the alignment film on the pixel electrode 5, a pretilt angle that is an inclination angle from the vertical direction of the liquid crystal molecules 7a is given. The pretilt angle of the liquid crystal molecules 7a can be set to 1 to 5 degrees, for example. In the liquid crystal display element 1, a pretilt angle can be similarly formed for the liquid crystal 7a in the vicinity of the counter electrode 6.

As the pretilt angle is set larger, the response speed of rising of the liquid crystal 7 can be increased, but the transmittance at OFF is increased and the contrast ratio of the display is deteriorated. Therefore, in the liquid crystal display element 1 of the present embodiment, it is preferable to set the pretilt angle within the range of 1 degree to 5 degrees as described above.

Such a pretilt angle can be formed using, for example, a PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open No. 2013-225102. In the PSA technique, a polymerizable component that is polymerized by light irradiation is mixed in a liquid crystal layer of a liquid crystal display element. Then, the polymerizable component is polymerized by driving the liquid crystal by applying a voltage between the electrodes of the liquid crystal display element and irradiating the liquid crystal display element with light in a state where the liquid crystal is tilted and aligned. As a result, the molecular orientation of the liquid crystal in the liquid crystal layer can be controlled by the mixed and polymerized polymerizable component, and a pretilt angle can be formed.

Therefore, in the liquid crystal display element 1, the formation of the pretilt angle as described above is held by the polymerized polymerizable component in the vicinity of the interface of the liquid crystal layer 4 with the alignment film.

Further, the liquid crystal display element 1 of the present embodiment has a pair of polarizing plates (illustrated) on each of the first substrate 2 and the second substrate 3 so as to form a crossed Nicol state with the liquid crystal layer 4 interposed therebetween. Is not arranged).

In the liquid crystal display element 1 of the present embodiment, when a voltage is applied to the liquid crystal layer 4 using the pixel electrode 5 and the counter electrode 6, the orientation of the liquid crystal 7 in the liquid crystal layer 4 changes, and the electric field in which the liquid crystal 7 is formed. , That is, the alignment direction of the liquid crystal 7 tends to be parallel to the substrate surface. At this time, in the liquid crystal display element 1, electric field distortion is generated by the uneven structure 10 on the surface of the pixel electrode 5, and an appropriate oblique electric field is formed between the pixel electrode 5 and the counter electrode 6. Therefore, the direction (tilt direction) of the orientation change of the liquid crystal 7 at the ON time is uniformly controlled in a desired direction by forming the oblique electric field due to the electric field distortion and the pretilt angle of the liquid crystal 7 described above.

As a result, in the portion where voltage is applied in the liquid crystal display element 1, the product of the refractive index anisotropy (Δn) of the liquid crystal 7 and the thickness (d) of the liquid crystal layer (Δn · The light transmission characteristic determined by d) changes. The liquid crystal display element 1 can constitute a normally black mode liquid crystal display element, and can perform a desired display by utilizing the property that the light transmission characteristic changes in the voltage application portion.

The above liquid crystal display element 1 is superior in response characteristics, has a low black display transmittance, and can realize a high contrast display as compared with a TN liquid crystal display element or an STN liquid crystal display element.

In the liquid crystal display element 1 of the present embodiment shown in FIG. 1, the counter electrode 6 is configured to have a flat surface. However, in the present invention, the counter electrode 6 may be any electrode that does not have electrode notches such as gaps and slits. For example, the same uneven structure as the pixel electrode 4 is formed on the surface on the liquid crystal layer 4 side. In addition, a step or the like may be formed. The counter electrode 6 can be provided as a common electrode common to a plurality of pixels.

Further, in the liquid crystal display element 1 of the present embodiment shown in FIG. 1, the pattern 11 extends in one direction and has a stripe-like structure as illustrated in FIG. Has a concavo-convex structure 10 on the surface derived from the shape of the pattern 11. However, in the present invention, the uneven structure on the surface of the pixel electrode is not limited to that illustrated in FIG. For example, each pixel can be divided into two or four, and a plurality of subpixels can be formed for each pixel, and the surface uneven structure can extend in different directions for each subpixel. In that case, it is preferable that the pattern disposed between the pixel electrode and the substrate is formed to extend in different directions for each region corresponding to each sub-pixel.

Further, when each pixel is divided into sub-pixels, it is preferable that the uneven structure on the electrode surface extends in a direction orthogonal to each other between adjacent sub-pixels. Therefore, it is preferable that the pattern disposed between the pixel electrode and the substrate is also formed so that a stripe-shaped structure extends in a direction orthogonal to each other between regions corresponding to adjacent subpixels.

Furthermore, in the second substrate 3, for example, a color filter in which red (R), green (G), and blue (B) filters are arranged between the second substrate 3 and the counter electrode 6. It is also possible to have (not shown). And as above-mentioned, when an uneven structure is formed in the surface of the counter electrode 6, it is preferable that a color filter is provided between the 2nd board | substrate 3 and the above-mentioned striped pattern. By having the color filter, the liquid crystal display element 1 of the present embodiment can perform color display.

The liquid crystal display element 1 of the above embodiment of the present invention can constitute an active matrix type liquid crystal display element.

In that case, for example, scanning lines (not shown) and signal lines (not shown) are wired in a matrix on the first substrate 2 of the liquid crystal display element 1, and at each intersection of the scanning lines and the signal lines. An active element (not shown) such as a TFT is arranged, and each pixel including the active element is formed.

The scanning line and the signal line are connected to a scanning driving circuit (not shown) and a signal driving circuit (not shown), respectively, and an arbitrary voltage can be applied to each scanning line or signal line. When the active element is a TFT, the drain electrode (not shown) of the TFT is connected to the signal line, and the source electrode (not shown) of the TFT is electrically connected to the pixel electrode 5 of each pixel, for example.

Further, a counter electrode 6 is provided on the entire surface of the second substrate 3. That is, the counter electrode 6 is configured to be a common electrode common to all of a plurality of pixels, and a common voltage is applied to all the pixels from a common voltage generation circuit (not shown).

In the liquid crystal display element 1 according to the embodiment of the present invention, a voltage is applied between the pixel electrode 5 disposed in each pixel of the first substrate 2 and the counter electrode 6 formed on the entire surface of the second substrate 3. As a result, the liquid crystal 7 of the liquid crystal layer 4 is driven to change the alignment. As described above, desired light can be displayed by controlling the light transmitted through the liquid crystal display element 1.

In the liquid crystal display element 1 of the present embodiment having the structure described above, the concavo-convex structure 10 on the surface of the pixel electrode 5 is an important component. In the liquid crystal display element 1 of the present embodiment, the concavo-convex structure 10 on the surface of the pixel electrode 5 has the shape of the pattern 11 made of resin disposed between the first substrate 2 and the pixel electrode 5 as described above. Derived from.

Therefore, in the liquid crystal display element 1 of this embodiment, when the uneven structure 10 on the surface of the pixel electrode 5 is to be formed in a desired shape in a highly uniform and simple manner, the formation of the pattern 11 is important. That is, it is preferable that the pattern 11 is easily formed by patterning with high uniformity.

Hereinafter, the formation of the uneven structure 10 on the surface of the pixel electrode 5 of the liquid crystal display element 1 according to the embodiment of the present invention will be described in more detail. In particular, a radiation-sensitive resin composition that is preferably used to form a resin pattern 11 disposed between the first substrate 2 and the pixel electrode 5 of the liquid crystal display element 1 will be described. In the liquid crystal display element 1 according to the embodiment of the present invention, the use of the radiation-sensitive resin composition according to the embodiment of the present invention for pattern formation eliminates the need for complicated operations such as dry etching. And the uneven structure on the surface of the pixel electrode can be easily realized by the simple formation of the pattern.

<Radiation sensitive resin composition>
In the liquid crystal display element according to the embodiment of the present invention, the radiation-sensitive resin composition according to the embodiment of the present invention is used for forming a pattern made of a resin for forming an uneven structure on the surface of the pixel electrode. That is, the coating film is formed on a suitable substrate using the radiation-sensitive resin composition of the embodiment of the present invention, patterned using radiation sensitivity, and made of a resin on the substrate as a cured film. A pattern can be formed.

The radiation-sensitive resin composition of the embodiment of the present invention contains [A] an alkali-soluble resin and [B] a photosensitizer. The radiation sensitive resin composition of this embodiment has radiation sensitivity. Moreover, unless the radiation sensitive resin composition of this embodiment impairs the effect of this invention, you may contain another arbitrary component.

The radiation-sensitive resin composition of the embodiment of the present invention includes a radiation-sensitive resin composition for forming a positive pattern in which a portion irradiated with light is dissolved by development, and a negative in which a portion irradiated with light is insolubilized. Any of the radiation sensitive resin compositions for forming the mold pattern can be applied.

In the radiation-sensitive resin composition for forming a positive pattern, [B-2] photoacid generator can be used as the [B] photosensitive agent which is the [B] component. In the radiation-sensitive resin composition for forming a negative pattern, [B-1] photo radical polymerization initiator can be used as the [B] photosensitive agent that is the [B] component.

That is, the radiation-sensitive resin composition of the embodiment of the present invention has at least one selected from [B-1] photoradical polymerization initiator and [B-2] photoacid generator as [B] photosensitizer. Can be used for negative pattern formation or positive pattern formation.

The radiation sensitive resin composition of the present embodiment has radiation sensitivity as described above. Then, by exposure and development using radiation sensitivity, a fine and elaborate striped pattern can be easily formed as a cured film, and a pattern suitable for forming a concavo-convex structure on the surface of the pixel electrode is obtained. Can be formed. That is, the radiation-sensitive resin composition of the present embodiment can form a resin pattern placed between a pixel electrode and a substrate provided with the pixel electrode with high accuracy.

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

<[A] alkali-soluble resin>
The radiation sensitive resin composition of the embodiment of the present invention contains [A] an alkali-soluble resin as an essential component.
The [A] alkali-soluble resin contained in the radiation-sensitive resin composition of the present embodiment is a resin that is soluble in an alkaline solvent and is a resin having alkali developability. [A] The alkali-soluble resin is preferably one selected from, for example, an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin. Hereinafter, each of [A] an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolak resin, which are preferable as the alkali-soluble resin, will be described in more detail.

[Acrylic resin having carboxyl group]
[A] The acrylic resin having a carboxyl group, which is preferable as the alkali-soluble resin, preferably contains a structural unit having a carboxyl group and a structural unit having a polymerizable group. In that case, it is not particularly limited as long as it includes a structural unit having a carboxyl group and a structural unit having a polymerizable group and has alkali developability (alkali solubility).

The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. When the acrylic resin having a carboxyl group contains the specific structural unit, a cured film having excellent surface curability and deep part curability is formed, and the surface of the pixel electrode of the liquid crystal display element of the embodiment of the present invention is formed. A pattern that realizes a concavo-convex structure can be formed.

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

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

The acrylic resin having a carboxyl group is, for example, copolymerizing a compound (A1) that gives a carboxyl group-containing structural unit and a compound (A2) that gives an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) may be further added to form a copolymer. Further, in the production of an acrylic resin having a carboxyl group, the (A4) compound (the (A1) compound, the (A2) compound and the (A3) described above) together with the above (A1) compound, (A2) compound and (A3) compound. Further, an unsaturated compound that gives structural units other than the structural unit derived from the compound) can be added to make a copolymer. Next, each compound of (A1) to (A3) will be described in detail.

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

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

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

Examples of anhydrides of unsaturated dicarboxylic acids include the anhydrides of the compounds exemplified as the dicarboxylic acid.

Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
These (A1) compounds may be used alone or in combination of two or more.

The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10% by mass to 25% by mass is more preferable. (A1) By using the compound in a proportion of 5% by mass to 30% by mass, it is possible to optimize the solubility of the acrylic resin having a carboxyl group in an alkaline aqueous solution and to form a film having excellent radiation sensitivity. .

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

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. Epoxy heptyl, methacrylic acid 6,7-epoxy heptyl, α-ethylacrylic acid-6,7-epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and the like are preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the cured film to be obtained.

As an unsaturated compound having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyl oxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

Of these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable.
These (A2) compounds may be used alone or in combination of two or more.

The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass% to 50 mass% is more preferable. By setting the proportion of the compound (A2) to be 5% by mass to 60% by mass, a cured film having excellent curability and the like can be formed, and a pattern made of a resin can be formed on the substrate.

((A3) Compound)
Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.

Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable.
These (A3) compounds may be used alone or in admixture of two or more.

The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass based on the total of the compound (A1), the compound (A2) and the compound (A3) (optional (A4) compound if necessary). 5% by mass to 25% by mass is more preferable.

((A4) Compound)
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. Examples of (A4) compounds include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the cyclic alkyl ester of acrylic acid include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate]. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.

These (A4) compounds may be used alone or in combination of two or more.

The use ratio of the (A4) compound is preferably 10% by mass to 80% by mass based on the total of the (A1) compound, the (A2) compound and the (A4) compound (and any (A3) compound).

[Polyimide resin]
The polyimide resin preferable as the [A] alkali-soluble resin used in the radiation-sensitive resin composition of the present embodiment is selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in the structural unit of the polymer. It is a polyimide resin having at least one kind. Having these alkali-soluble groups in the structural unit provides alkali developability (alkali-solubility), and can suppress the occurrence of scum in the exposed area during alkali development.

In addition, it is preferable that the polyimide resin has a fluorine atom in the structural unit, since water repellency is imparted to the interface of the film and development of the interface is suppressed when developing with an alkaline aqueous solution. The fluorine atom content in the polyimide resin is preferably 10% by mass or more in order to sufficiently obtain the effect of preventing the penetration of the interface, and is preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

The polyimide resin preferable as [A] alkali-soluble resin used for the radiation sensitive resin composition of this embodiment is a polyimide resin obtained by condensing an acid component and an amine component, for example. Tetracarboxylic dianhydride is preferably selected as the acid component, and diamine is preferably selected as the amine component.
[A] The structure of the polyimide resin preferable as the alkali-soluble resin is not particularly limited, but preferably has a structural unit represented by the following formula (1).

In the above formula (1), R ¹ represents a tetravalent to 14-valent organic group, and R ² represents a divalent to 12-valent organic group. R ³ and R ⁴ represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and may be the same or different. a and b each represents an integer of 0 to 10.

In the above formula (1), R ¹ represents a residue of tetracarboxylic dianhydride used for forming the polyimide resin, and is a tetravalent to 14-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

Examples of the tetracarboxylic dianhydride used for forming the polyimide resin include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2 , 3- Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9 -Bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene dianhydride or acid dianhydride having the structure shown below is preferred. Two or more of these may be used.

R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ⁶ and R ⁷ represent a hydrogen atom, a hydroxyl group or a thiol group.

In the above formula (1), R ² represents the residue of the diamine used for forming the polyimide resin, and is a divalent to 12-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

Specific examples of the diamine used for forming the polyimide resin include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis ( 4-aminophenyl) fluorene or shown below Diamine or the like of the structure is preferable. Two or more of these may be used.

R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ⁶ to R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.

In addition, in order to improve the adhesiveness between the pattern formed on the substrate and the substrate formed after forming the coating film of the radiation sensitive resin composition of the present embodiment on the substrate, R ^{1 is used} within the range not reducing the heat resistance. or it may be copolymerized aliphatic groups with a siloxane structure into R ^2. Specifically, examples of the diamine as an amine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc., which are copolymerized in an amount of 1 mol% to 10 mol%. Can be mentioned.

In the above formula (1), R ³ and R ⁴ represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group. a and b each represents an integer of 0 to 10. Although a and b are preferably 0 from the stability of the resulting radiation-sensitive resin composition, a and b are preferably 1 or more from the viewpoint of solubility in an aqueous alkali solution.

By adjusting the amount of the alkali-soluble group of R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a radiation-sensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

In the case where both R ³ and R ⁴ are phenolic hydroxyl groups, in order to make the dissolution rate in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution more suitable, The phenolic hydroxyl group content is preferably 2 to 4 mol per kg of (a). By setting the amount of phenolic hydroxyl group within this range, a radiation-sensitive resin composition with higher sensitivity and contrast can be obtained.

The polyimide having the structural unit represented by the above formula (1) preferably has an alkali-soluble group at the end of the main chain. Such polyimide has high alkali solubility. Specific examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Introduction of an alkali-soluble group at the end of the main chain can be carried out by imparting an alkali-soluble group to the end capping agent. As the terminal capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.

Monoamines used as end capping agents include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-a Nosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds used as end-capping agents include phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid Acid anhydrides such as acid anhydrides, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Nocarboxylic acids and monoacid chloride compounds in which these carboxyl groups are acid chlorides, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Mono-acid chloride compounds in which only one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chloride, mono-acid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5-norbornene- Active ester compounds obtained by reaction with 2,3-dicarboximide are preferred. Two or more of these may be used.

The introduction ratio of the monoamine used for the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

In the polyimide resin having the structural unit represented by the above formula (1), the number of repeating structural units is preferably 3 or more, more preferably 5 or more, and preferably 200 or less, more preferably 100 or less. If it is this range, the cured film of the desired film thickness can be formed using the photosensitive resin composition of this embodiment, and the pattern which consists of resin of a desired shape can be formed.

In the present embodiment, [A] a polyimide resin preferable as the alkali-soluble resin may be composed only of the structural unit represented by the above formula (1), or may be a copolymer or a mixture with other structural units. It may be a body. In that case, it is preferable to contain the structural unit represented by General formula (1) 10 mass% or more of the whole polyimide resin. If it is 10 mass% or more, the shrinkage | contraction at the time of thermosetting can be suppressed, and it is suitable for preparation of a comparatively thick pattern especially. The type and amount of the structural unit used for copolymerization or mixing is preferably selected within a range that does not impair the heat resistance of the polyimide resin obtained by the final heat treatment. Examples include benzoxazole, benzimidazole, and benzothiazole. These structural units are preferably 70% by mass or less in the polyimide resin.

In this embodiment, a preferable polyimide resin can be synthesized using a method of obtaining a polyimide precursor using a known method and imidizing it using a known imidization reaction method, for example. As a known synthesis method of the polyimide precursor, a part of the diamine is replaced with a monoamine which is a terminal blocking agent, or a part of the acid dianhydride is a monocarboxylic acid or an acid anhydride which is a terminal blocking agent. It can be obtained by reacting an amine component and an acid component in place of a monoacid chloride compound or a monoactive ester compound. For example, a method of reacting tetracarboxylic dianhydride and diamine (partially substituted with monoamine) at low temperature, tetracarboxylic dianhydride (partially acid anhydride, monoacid chloride compound or monoactivity at low temperature) A method in which an ester compound is substituted) and a diamine, a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then a reaction is performed in the presence of a diamine (partially substituted with a monoamine) and a condensing agent, tetracarboxylic acid There is a method in which a diester is obtained with a dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with a diamine (partially substituted with a monoamine).

Moreover, the imidation ratio of the polyimide resin of this embodiment can be easily calculated | required with the following method, for example. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, the polymer was heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum was measured, and the peak intensity around 1377 cm ⁻¹ was compared to calculate the content of imide groups in the polymer before heat treatment. Find the rate.

In this embodiment, the imidation ratio of the polyimide resin is preferably 80% or more from the viewpoint of chemical resistance and a high shrinkage residual film ratio.

Further, the end-capping agent introduced into the preferred polyimide resin in the present embodiment can be easily detected by the following method. For example, a polyimide resin introduced with a terminal blocking agent is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polyimide resin, and this is measured by gas chromatography (GC) or NMR. Thus, the end-capping agent used for forming the polyimide resin can be easily detected. Apart from this, it can also be easily detected by directly measuring the polymer component into which the end-capping agent has been introduced, by pyrolysis gas chromatography (PGC), infrared spectrum and 13C-NMR spectrum.

[Polysiloxane]
A preferred polysiloxane as a resin used in the radiation sensitive resin composition of the present embodiment is a polysiloxane having a radical reactive functional group. When the polysiloxane is a polysiloxane having a radical reactive functional group, the polysiloxane is not particularly limited as long as it has a radical reactive functional group in the main chain or side chain of a polymer having a siloxane bond. In that case, the polysiloxane can be cured by radical polymerization, and cure shrinkage can be minimized. Examples of the radical reactive functional group include unsaturated organic groups such as a vinyl group, α-methylvinyl group, acryloyl group, methacryloyl group, and styryl group. Among these, those having an acryloyl group or a methacryloyl group are preferable because the curing reaction proceeds smoothly.

In the present embodiment, the preferred polysiloxane is preferably a hydrolytic condensate of a hydrolyzable silane compound. The hydrolyzable silane compound constituting the polysiloxane includes (s1) a hydrolyzable silane compound represented by the following formula (2-1) (hereinafter also referred to as (s1) compound), and (s2) the following formula (2 -2) and a hydrolyzable silane compound (hereinafter also referred to as (s2) compound).

In the above formula (2-1), R ¹¹ is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3. ^{However, if R 11} and ^{R 12} is plural, ^{R 11} and ^{R 12} are each, independently.

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

In the present invention, the “hydrolyzable silane compound” is usually hydrolyzed by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a catalyst and excess water. It refers to a compound having a group capable of forming a silanol group or a group capable of forming a siloxane condensate. In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (2-1) and the above formula (2-2), some hydrolyzable groups are not hydrolyzed in the resulting polysiloxane. It may remain in the state. Here, the “hydrolyzable group” refers to a group capable of forming a silanol group upon hydrolysis as described above or a group capable of forming a siloxane condensate. In addition, in the radiation-sensitive resin composition of the present embodiment, some hydrolyzable silane compounds are in a state in which some or all of the hydrolyzable groups in the molecule are unhydrolyzed, and other It may remain in a monomer state without being condensed with the hydrolyzable silane compound. The “hydrolysis condensate” means a hydrolysis condensate obtained by condensing some silanol groups of a hydrolyzed silane compound.
Hereinafter, the (s1) compound and the (s2) compound will be described in detail.

((S1) compound)
In the above formula (2-1), R ¹¹ is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3. ^{However, if R 11} and ^{R 12} is plural, ^{R 11} and ^{R 12} are each, independently.
Examples of the alkyl group having 1 to 6 carbon atoms as R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. As said p, 1 or 2 is preferable from a viewpoint of progress of a hydrolysis condensation reaction, and 1 is more preferable.

Examples of the organic group having a radical reactive functional group include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with the above radical reactive functional group, And an aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms. When a plurality of R ¹² are present in the same molecule, these are independent of each other. Further, the organic group represented by R ¹² may have a hetero atom. Examples of such an organic group include an ether group, an ester group, and a sulfide group.

Examples of the compound (s1) in the case of p = 1 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, and m-styryltrimethoxysilane. M-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxytrimethoxysilane, methacryloxytriethoxysilane, methacryloxytripropoxysilane, Acryloxytrimethoxysilane, acryloxytriethoxysilane, acryloxytripropoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane 2-methacryloxyethyl tripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyl Triethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane , Trifluorobutyl trimethoxysilane, 3-trialkoxysilane compounds such as (trimethoxysilyl) propyl succinic anhydride and the like.

Examples of the compound (s1) in the case of p = 2 include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, phenyltri And dialkoxysilane compounds such as fluoropropyldimethoxysilane.

Examples of the compound (s1) when p = 3 include allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-acryloxypropyldimethyl. Methoxysilane, 3-methacryloxypropyldiphenylmethoxysilane, 3-acryloxypropyldiphenylmethoxysilane, 3,3′-dimethacryloxypropyldimethoxysilane, 3,3′-diaacryloxypropyldimethoxysilane, 3,3 ′, Monoalkoxysilane compounds such as 3 ″ -trimethacryloxypropylmethoxysilane, 3,3 ′, 3 ″ -triacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxysilane, etc. And the like.

Among these (s1) compounds, the scratch resistance and the like can be achieved at a high level, and the condensation reactivity is enhanced. Therefore, vinyltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, and 3- (trimethoxysilyl) propyl succinic anhydride are preferred.

((S2) compound)
In the above formula (2-2), R ¹³ is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group, or an isocyanate group. n is an integer of 0-20. q is an integer of 0 to 3. ^{However, if R 13} and ^{R 14} is each one, the plurality of ^{R 13} and ^{R 14} are each, independently.

Examples of the alkyl group having 1 to 6 carbon atoms as R ¹³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. As said q, 1 or 2 is preferable from a viewpoint of progress of a hydrolysis condensation reaction, and 1 is more preferable.

When R ¹⁴ is an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. Group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl Group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2- Dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methyl Tylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethyl Butyl group, 1,2,3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1- Methylheptyl group, 2-ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n Heptadecyl, n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like. An alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.

As the compound (s2) in the case of q = 0, for example, as a silane compound substituted with four hydrolyzable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, tetra -I-propoxysilane and the like.

As the compound (s2) in the case of q = 1, as a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, for example, methyltrimethoxysilane, methyltriethoxysilane, Methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphthyl Trimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxysila , 3-isocyanoacetate trimethoxysilane, 3-isocyanoacetate triethoxysilane o- tolyl trimethoxysilane, m- tolyl trimethoxysilane p- tolyl trimethoxysilane, and the like.

As the compound (s2) in the case of q = 2, examples of the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, and ditolyl. Examples include dimethoxysilane and dibutyldimethoxysilane.

As the compound (s2) in the case of q = 3, examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include trimethylmethoxysilane, triphenylmethoxysilane, Examples include tolylmethoxysilane and tributylmethoxysilane.

Of these (s2) compounds, a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is preferred. More preferred are silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups.

Particularly preferred hydrolyzable silane compounds include, for example, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, ethyltrisilane. Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, naphthyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-isocyanate And propyltrimethoxysilane. Such hydrolyzable silane compounds may be used alone or in combination of two or more.

Regarding the mixing ratio of the compound (s1) and the compound (s2), it is desirable that the compound (s1) exceeds 5 mol%. When the compound (s1) is 5 mol% or less, the exposure sensitivity when forming a pattern from the coating film is low, and the scratch resistance and the like of the resulting pattern tend to be reduced.

(Hydrolytic condensation of (s1) compound and (s2) compound)
The conditions for hydrolyzing and condensing the compound (s1) and the compound (s2) include hydrolyzing at least a part of the compound (s1) and the compound (s2) to convert a hydrolyzable group into a silanol group and condensing the compound. Although it will not specifically limit as long as it raise | generates reaction, As an example, it can implement as follows.

It is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like as water used for the hydrolysis condensation reaction. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably from 0.1 mol to 3 mol, more preferably from 0.3 mol to 2 mol, based on 1 mol of the total amount of the hydrolyzable groups of the compounds (s1) and (s2). Particularly preferred is 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

Examples of the solvent used for hydrolysis condensation include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers. Examples include propionates, aromatic hydrocarbons, ketones, and other esters. These solvents can be used alone or in combination of two or more.

Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred. Particularly, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate. , Propylene glycol monomethyl ether and butyl methoxyacetate are preferred.

The hydrolysis condensation reaction is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids, etc.), base Catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; Carboxylic acid salts such as sodium acetate; various Lewis bases) or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide, etc.) are used in the presence of a catalyst. For example, tri-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0.001 mol per mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction. 1 mole.

The weight-average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene by GPC (gel permeation chromatography) of the above-mentioned hydrolysis condensate is preferably 500 to 10,000, more preferably 1,000 to 5,000. By making Mw 500 or more, the film formability of the radiation sensitive resin composition of the present embodiment can be improved. On the other hand, by setting Mw to 10,000 or less, it is possible to prevent the developability of the radiation-sensitive resin composition from decreasing.

The polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) by GPC of the hydrolysis condensate described above is preferably 300 to 5000, more preferably 500 to 3000. By making Mn of polysiloxane into the said range, the cure reactivity at the time of hardening of the coating film of the radiation sensitive resin composition of this embodiment can be improved.

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

[Novolac resin]
A novolak resin preferable as a resin used in the radiation-sensitive resin composition of the present embodiment can be obtained by polycondensing phenols with aldehydes such as formalin by a known method.

Examples of phenols for obtaining a novolak resin preferable in the radiation-sensitive resin composition of the present embodiment include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, and 2,4-dimethylphenol. 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, 2,4,5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chloro Phenol, 2,3-dichloro Enol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol , Α-naphthol, β-naphthol and the like. Two or more of these may be used.

In the radiation-sensitive resin composition of the present embodiment, examples of aldehydes for obtaining a preferred novolak resin include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like in addition to formalin. Two or more of these may be used.

The weight average molecular weight of the novolak resin preferable as the [A] alkali-soluble resin contained in the radiation-sensitive resin composition of the present embodiment is preferably 2000 to 50000 in terms of polystyrene by GPC (gel permeation chromatography), more preferably. Is 3000 to 40000.

<[B] Photosensitive agent>
[B] Photosensitizer contained in the radiation-sensitive resin composition of the embodiment of the present invention includes a compound capable of initiating polymerization by generating radicals in response to radiation (that is, [B-1] initiation of photoradical polymerization. Agent) or a compound that generates an acid in response to radiation (that is, [B-2] photoacid generator).

Examples of such [B-1] photoradical polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds and the like. These compounds may be used alone or in combination of two or more.

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

Of these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

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

Examples of α-aminoketone compounds include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.

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

The acetophenone compound is preferably an α-aminoketone compound, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are preferred.

Examples of the biimidazole 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 or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5′-Tetraphenyl-1,2′-biimidazole is preferred, of which 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is more preferred.

[B-1] The radical photopolymerization initiator can be used alone or in admixture of two or more as described above. [B-1] The content ratio of the photo radical polymerization initiator is preferably 1 part by mass to 40 parts by mass and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the [A] alkali-soluble resin. [B-1] By using the photo-radical polymerization initiator in a proportion of 1 to 40 parts by mass, the radiation-sensitive resin composition has a high solvent resistance, a high hardness, and a low exposure amount. A cured film having high adhesion can be formed. As a result, a pattern made of a resin excellent in such characteristics can be provided.

Next, [B-2] photoacid generator that is [B] photosensitizer of the radiation sensitive resin composition of the present embodiment includes, for example, oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, Examples include diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinonediazide compounds. These [B-2] photoacid generators may be used alone or in combination of two or more.

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (3) is preferable.

In the above formula (3), R ^a is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

The alkyl group represented by R ^a in the above formula (3) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- And alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

The alicyclic hydrocarbon group represented by R ^a is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ^a is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

Specific examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2- Ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2- Examples include ylidene)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like, which are commercially available.

Examples of the onium salt described above include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and benzylsulfonium salt.

As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Phosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferred.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) dipheny Maleimide, N-(4-methylphenyl-sulfonyloxy) include diphenyl maleimides and the like.

Preferable examples of the sulfonic acid ester compound include haloalkyl sulfonic acid esters, and more preferable examples include N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester.

As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide or 1,2-naphthoquinonediazidesulfonic acid amide is used. Can be used.

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

As a specific example of the above mother nucleus, for example,
Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
As pentahydroxybenzophenone, 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
As hexahydroxybenzophenone, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone, etc .;
(Polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4- Hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4 -Hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6 , 7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan, etc .;
Can be mentioned.

Examples of the other mother nucleus include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1 -(4-Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl } -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

Among these, as the mother nucleus, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [ 1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride, and 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5- Sulfonic acid chloride is more preferred, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

As the above-mentioned 1,2-naphthoquinone diazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide is preferable.

In the condensation reaction of the above-mentioned phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to an amount of not less than 85% and not more than 85 mol%, more preferably not less than 50 mol% and not more than 70 mol% can be used. In addition, the said condensation reaction can be implemented by a well-known method.

As the above [B-2] photoacid generator, an oxime sulfonate compound, an onium salt, a sulfonimide compound, and a quinonediazide compound are preferable, and an oxime sulfonate compound and a quinonediazide compound are more preferable.
[B-2] By using the above-mentioned compound as the photoacid generator, the radiation-sensitive resin composition of the present embodiment containing the compound can improve sensitivity and solubility.

[B-2] The content of the photoacid generator is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of [A] alkali-soluble resin. . [B-2] By setting the content of the photoacid generator in the above range, the sensitivity of the radiation-sensitive resin composition of the present embodiment can be optimized, and a cured film having a high surface hardness can be formed. Patterns can be provided.

<Optional component>
The radiation-sensitive resin composition of the present embodiment includes [C] a polyfunctional acrylate and [C] a polyfunctional acrylate, if necessary, in addition to [A] alkali-soluble resin and [B] photosensitizer. [D] In addition to the chain transfer agent, other optional components such as a surfactant can be contained. Two or more optional components may be mixed and used. Hereinafter, each optional component will be described.

[[C] polyfunctional acrylate]
The radiation sensitive resin composition of this embodiment can contain the polymeric compound which has several (meth) acryloyl group in a molecule | numerator as polyfunctional acrylate. One of the functions of this polymerizable compound is to polymerize and form a high molecular weight or to form a crosslinked structure when the radiation sensitive resin composition is irradiated with light as radiation. By containing such a polymerizable compound, the entire coating film of the radiation-sensitive resin composition of the present embodiment can be cured to form a cured film. And the contrast of a light irradiation part and the part which is not so can be improved, prevention of peeling at the time of image development, and formation of a residue can be suppressed.

Here, “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, and “having a plurality of (meth) acryloyl groups in a molecule” means an acryloyl group present in the molecule. The total of group and methacryloyl group is 2 or more. In that case, the total number of these groups should just be 2 or more, and either an acryloyl group and a methacryloyl group do not need to exist.

Examples of the polymerizable compound having a plurality of (meth) acryloyl groups in the molecule include the following.

Examples of the polymerizable compound having two (meth) acryloyl groups in the molecule include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) Acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethyl Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, full orange (meth) acrylate, hydroxypivalin Acid neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, oligopropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, bis (2- Rokishiechiru) isocyanurate di (meth) acrylate.

Examples of polymerizable compounds having three (meth) acryloyl groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( (Meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol propionate tri (meth) acrylate, tri ((meth) acryloyloxy) Ethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

Polymerizable compounds having four (meth) acryloyl groups in the molecule include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetrapropionate (meth). ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol triacrylate and the like.

Examples of the polymerizable compound having five (meth) acryloyl groups in the molecule include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Examples of polymerizable compounds having six (meth) acryloyl groups in the molecule include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and caprolactone-modified dipentaerythritol. Examples include hexa (meth) acrylate.

[C] The polyfunctional acrylate may be a polymerizable compound having seven or more (meth) acryloyl groups. [C] The polyfunctional acrylate may be (meth) acrylates having a hydroxyl group among the above-described polymerizable compounds, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups. Good. Furthermore, as [C] polyfunctional acrylate, as long as it is a compound having two or more (meth) acryloyl groups, oligoester (meth) acrylates, oligoether (meth) acrylates, and oligoepoxy (meth) acrylates Etc. can be used.

Among these [C] polyfunctional acrylates, among these, pentaerythritol tri (meth) acrylate, full orange (meth) acrylate, oligoester (meth) acrylate (dendrimer (meth) acrylate) are excellent in polymerizability. More preferred.

With respect to the commercially available products of the polymerizable compounds exemplified as the [C] polyfunctional acrylate as described above, for example, Aronix (registered trademark) M-400, M-404, M-408, M-450, M manufactured by Toagosei Co., Ltd. -305, M-309, M-310, M-313, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225 M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO -924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, TO-1450, TO-1382 KAYARAD (registered trademark) D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR manufactured by Nippon Kayaku Co., Ltd. -355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035 SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR -9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG 00DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. Light Acrylate® PE-4A, DPE-6A, DTMP-4A, Osaka Organic Chemical Industry Co., Ltd. Biscoat # 802; And a mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate.

The content of [C] polyfunctional acrylate in the radiation-sensitive resin composition of the present embodiment is preferably 1% by mass to 20% by mass with respect to the whole radiation-sensitive resin composition. Moreover, when the radiation sensitive resin composition of this embodiment contains an organic solvent, the content of the [C] polyfunctional acrylate polymerizable compound in the radiation sensitive resin composition is the sum of the components excluding the organic solvent. On the other hand, it is preferably in the range of 5% by mass to 50% by mass or less, and more preferably in the range of 10% by mass to 40% by mass. [C] By containing the polyfunctional acrylate in the above range, a cured film with high hardness can be obtained using the radiation-sensitive resin composition of the present embodiment, and a pattern with high hardness made of resin can be obtained. Can do.

[[D] chain transfer agent]
Conventionally, by using a resin composition having radiation sensitivity, a cured film can be formed from the coating film and patterned to obtain a resin pattern. However, when the cured film is, for example, a thin film of about 1 μm or less and is radically curable, curing tends to be insufficient. If the cured film is insufficiently cured, it tends to cause development peeling at the time of patterning.

For this reason, the present inventor has studied to improve the curing performance using the radiation-sensitive resin composition of the present embodiment, and as a result, has found that a chain transfer agent is effective in improving curability. That is, in the radiation sensitive resin composition of this embodiment, a [D] chain transfer agent can be contained as arbitrary [D] components. A chain transfer reaction is a reaction in which radicals of a growing polymer chain move to another molecule in radical polymerization, and a chain transfer agent is an agent that causes a chain transfer reaction. The radiation sensitive resin composition of the present embodiment can be provided with sufficiently high curability even if it is a cured film of a thin film of 1 μm or less, for example, by containing a [D] chain transfer agent, It is suitable for forming a pattern having a desired shape.

[D] The chain transfer agent contained in the radiation-sensitive resin composition of the present embodiment is not particularly limited as long as it is a compound that functions as a chain transfer agent in a radical polymerization reaction. Examples of the [D] chain transfer agent that is preferably contained in the radiation-sensitive resin composition of the present embodiment include those containing pyrazole derivatives, alkylthiols and the like.

And as a preferable [D] chain transfer agent, what contains the compound etc. which have a mercapto group (thiol group) etc. can be mentioned, for example, As a more preferable [D] chain transfer agent, 2 in 1 molecule The thing containing the compound etc. which have the above mercapto groups can be mentioned.

[D] A compound having two or more mercapto groups in one molecule that is preferably contained in the chain transfer agent is not particularly limited as long as it has two or more mercapto groups in one molecule. For example, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (4) can be mentioned.

In the formula (4), R ³¹ is a methylene group or an alkylene group having 2 to 10 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted with alkyl groups. Y ¹ is a single bond, —CO— or —O—CO— ^* . However, bond binds to ^{R 31} marked with *. n is an integer of 2 to 10. A ¹ is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or a group represented by the following formula (5) when n is 3. .

In the above formula (5), R ³² to R ³⁴ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms. “*” Represents a bond.

As the compound represented by the above formula (4), typically an esterified product of mercaptocarboxylic acid and polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Examples of the polyhydric alcohol constituting the esterified product include ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, pentaerythritol and the like.

Examples of the compound represented by the above formula (4) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate). Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptopentylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione preferable.

As the compound having two or more mercapto groups in one molecule of the thiol compound, compounds represented by the following formulas (6) to (8) can also be used.

In the above formula (6), R ⁴¹ is a methylene group or an alkylene group having 2 to 20 carbon atoms. R ⁴² is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms. k is an integer of 1 to 20.

In the above formula (7), R ⁴³ to R ⁴⁶ are each independently a hydrogen atom, a hydroxyl group or a group represented by the following formula (8). However, at least one of R ⁴³ to R ⁴⁶ is a group represented by the following formula (8).

In the above formula (8), R ⁴⁷ is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms.

In the radiation-sensitive resin composition of the present embodiment, the [D] chain transfer agent can be used alone or in combination of two or more. The content ratio of the [D] chain transfer agent in the radiation-sensitive resin composition is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the [A] alkali-soluble resin, and 1 to 15 parts by mass. Part is more preferred. [D] When the amount of the chain transfer agent used is less than 0.5 parts by weight, the effect of improving the curability cannot be sufficiently obtained. When the amount exceeds 20 parts by weight, the sensitivity becomes too sensitive and the light leaks. There is a possibility that the pattern shape may be damaged by increasing the curability.

[Surfactant]
The surfactant contained in the radiation-sensitive resin composition of the present embodiment is added to improve the coating property of the radiation-sensitive resin composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. Can do. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 , 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-he Fluoroalkanes such as safluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxy Rates: Fluorine alkyl esters and the like can be mentioned.

Commercially available products of these fluorosurfactants include F-top (registered trademark) EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFac (registered trademark) F171, 172, 173 (DIC Corporation). Manufactured), FLORARD FC430, 431 (manufactured by Sumitomo 3M), Asahi Guard AG (registered trademark) 710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC-101, 102, 103, 104 105, 106 (manufactured by AGC Seimi Chemical Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.), and the like.

Examples of silicone-based surfactants are the commercial names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.).

When a surfactant is used as an optional component, the content thereof is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass with respect to 100 parts by mass of [A] alkali-soluble resin. The amount is 5 parts by mass or less. By making the usage-amount of surfactant into 0.01 mass part or more and 10 mass parts or less, the applicability | paintability of the radiation sensitive resin composition of this embodiment can be optimized.

<Preparation of radiation-sensitive resin composition>
Next, preparation of the radiation sensitive resin composition of this invention is demonstrated.

In addition to [A] alkali-soluble resin and [B] photosensitizer, the radiation-sensitive resin composition of the present embodiment includes [C] polyfunctional acrylate, [D] chain transfer agent, surfactant and the like as necessary. It is prepared by mixing other optional ingredients. At this time, an organic solvent can be used to prepare a liquid radiation-sensitive resin composition. An organic solvent can be used individually or in mixture of 2 or more types.

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

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

For example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene Esters such as glycol monoethyl ether acetate and methyl-3-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; benzene, Aromatic hydrocarbons such as toluene and xylene; dimethylformamide; Methylacetamide, etc. amides such as N- methylpyrrolidone.

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

Next, formation of a pattern using the radiation-sensitive resin composition of the present embodiment and formation of a concavo-convex structure on the surface of the pixel electrode by the pattern will be described.

<Formation of pattern and concavo-convex structure>
In the formation of a pattern using the radiation-sensitive resin composition of the present embodiment and the formation of the concavo-convex structure on the substrate surface on which the pixel electrode is formed by the pattern, the following steps [1] to [4] are performed. It is preferable to include in this order.

[1] A step of forming a coating film of a radiation-sensitive resin composition containing [A] alkali-soluble resin and [B] photosensitizer on a substrate (hereinafter, referred to as “step [1]”). ). Note that an active element such as a TFT, an electrode, a wiring, or the like may be formed on the substrate in this step.

[2] A step of irradiating at least a part of the coating film of the radiation-sensitive resin composition formed in the step [1] (hereinafter sometimes referred to as “step [2]”).
[3] A step of developing the coating film irradiated with radiation in the step [2] to form a pattern (hereinafter sometimes referred to as “step [3]”).
[4] A step of providing a pixel electrode on the substrate on which the pattern is formed in the step [3] (hereinafter sometimes referred to as “step [4]”).

According to the steps [1] to [4], a pattern made of a resin can be disposed between the substrate and the pixel electrode, and an uneven structure having a desired shape can be easily formed on the surface of the substrate on the pixel electrode side. Can be formed.

In addition, it is also possible to provide the process of heating a pattern after process [3] and before process [4]. According to the composition of the radiation sensitive resin composition of the present embodiment, it is preferable to provide a step of heating the pattern if such heating is effective in improving characteristics such as the strength of the pattern.

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

[Step [1]]
At this process, the coating film of the radiation sensitive resin composition of embodiment of this invention is formed on a board | substrate. On this substrate, active elements, wirings, electrodes and the like are formed. These active elements and the like are formed according to a known method on a substrate by repeating a normal semiconductor film formation, a known insulating layer formation, etc., and etching by a photolithography method. It is also possible to use a substrate in which an inorganic insulating film made of a metal oxide such as SiO ₂ or a metal nitride such as SiN is formed on an active element or the like as the substrate.

After applying the radiation-sensitive resin composition of the embodiment of the present invention to the surface on which the active element or the like is formed on the substrate, pre-baking is performed to evaporate the solvent to form a coating film.

Examples of the substrate material include glass substrates such as soda lime glass and alkali-free glass, silicon substrates, and resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, and polyimide. Etc. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.

Examples of the coating method of the radiation sensitive resin composition include a spray method, a roll coating method, a spin coating method (sometimes called a spin coating method or a spinner method), and a slit coating method (slit die coating method). An appropriate method such as a bar coating method or an ink jet coating method can be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

The pre-baking conditions described above vary depending on the types and blending ratios of the components constituting the radiation-sensitive resin composition, but are preferably performed at a temperature of 70 ° C. to 120 ° C. The time is such as a hot plate or an oven. Although it depends on the heating device, it can be about 1 to 10 minutes.

[Step [2]]
Next, in this step, radiation is applied to at least a part of the coating film on the substrate formed in step [1]. In this case, when a part of the coating film is irradiated with radiation, it is preferably performed through a photomask having a predetermined mask pattern. For example, it is preferable to perform radiation irradiation through a photomask having a striped mask pattern.

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

The dose of radiation in the step [2], the intensity at the wavelength 365nm radiation, luminometer (OAI model356, OAI Optical Associates Ltd. Inc.) as a value measured by, preferably ^{100J / m 2 ~ 10000J / m} 2, more preferably ^{500J / m 2 ~ 6000J / m} 2.

[Step [3]]
Next, in this step, the irradiated film obtained in step [2] is developed to remove unnecessary portions and form a predetermined pattern as a cured film. When the coating film of the radiation sensitive resin composition to be used is a negative type, the non-irradiated part of radiation becomes an unnecessary part. Moreover, when the coating film of the radiation sensitive resin composition to be used is a positive type, the irradiation part of a radiation becomes an unnecessary part.

As the developer used in the development step of step [3], it is preferable to use an alkali developer composed of an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline developer. The concentration of alkali in the alkali developer is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.
For example, the pattern formed on the substrate can have a stripe structure in which a plurality of strip-shaped resin materials are arranged on the substrate at regular intervals.

As described above, since the pattern on the substrate formed by the steps [1] to [3] has high transparency and excellent curability, it can be made into a thin film.

The film thickness of the pattern is preferably 0.1 μm to 3 μm, more preferably 0.1 μm to 2 μm. That is, this pattern is formed using the radiation-sensitive resin composition of the present embodiment, and can exhibit excellent curability even with a film thickness of 1 μm or less, for example. Therefore, the film thickness of the particularly preferable pattern can be 0.1 μm to 1 μm.

[Step [4]]
Next, in this step, a pixel electrode is formed on the substrate on which the pattern is formed obtained in step [3] so as to cover the pattern. For example, a transparent conductive layer made of ITO can be formed on a substrate on which a pattern is formed using a sputtering method or the like. Next, the transparent conductive layer is etched using a photolithography method, and a pixel electrode having a predetermined shape can be formed as a transparent electrode on the substrate on which the pattern is formed. As described above, when an active element or the like is provided on the substrate, the pixel electrode is formed so as to be electrically connected to the active element.

In addition to the ITO, the pixel electrode can be configured using a transparent material having high transmittance and conductivity with respect to visible light. For example, a transparent conductive material such as zinc oxide-based AZO or GZO may be used.

As described above, the pattern on the substrate is formed in the above-described steps [1] to [3], whereby the pixel electrode formed on the substrate in step [4] has an uneven structure on the surface. be able to. That is, the pixel electrode formed on the substrate has a concavo-convex structure on the surface by arranging the pattern formed using the radiation-sensitive resin composition of the present embodiment between the pixel electrode and the substrate. Can do.

The concavo-convex structure on the surface of the pixel electrode has concave and convex surfaces alternately along a direction parallel to the substrate surface as illustrated in FIG. 1 described above, and a step portion between them is perpendicular to the substrate surface. The structure can be a vertical plane. At this time, the distance between the concave and convex surfaces of the concavo-convex structure, that is, the height difference in the concavo-convex structure 10 can be set to a desired value within the range of 0.1 μm to 2.0 μm. For example, the height difference in the concavo-convex structure 10 can be in the range of 0.1 μm to 1.0 μm.

And the liquid crystal display element constituted by using the substrate obtained by the steps [1] to [4] can have, for example, the structure illustrated in FIG. The liquid crystal display element can generate a desired electric field distortion in the liquid crystal layer when ON due to the concavo-convex structure on the surface of the pixel electrode, and can realize uniform liquid crystal orientation change when ON. it can. And the liquid crystal display element of embodiment of this invention becomes a VA-type liquid crystal display element which can be manufactured simply and suppressed the fall of display quality.

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

<Preparation of radiation-sensitive resin composition>
Synthesis example 1
[Synthesis of Resin (α-I)]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, 10 parts by weight of styrene, 12 parts by weight of tetrahydrofurfuryl methacrylate, 15 parts by weight of N-cyclohexylmaleimide and n- After charging 10 parts by mass of lauryl methacrylate and purging with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 5 hours. As a copolymer, a solution containing a resin (α-I), which is an alkali-soluble resin containing a carboxyl group and an epoxy group, was obtained. The Mw of the resin (α-I) as a copolymer was 8000.

Synthesis example 2
[Synthesis of Resin (α-II)]
Under a dry nitrogen stream, 29.30 g (0.08 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Central Glass), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1 .24 g (0.005 mol), 3.27 g (0.03 mol) of 3-aminophenol (Tokyo Chemical Industry Co., Ltd.) as an end-capping agent is N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Dissolved in 80 g. To this was added 31.2 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (Manac) together with 20 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then at 50 ° C. for 4 hours. Reacted. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a resin (α-II) which is a polyimide precursor resin as a polymer.

Synthesis example 3
[Synthesis of Resin (α-III)]
In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane, and heated until the solution temperature reached 60 ° C. . After the solution temperature reached 60 ° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 4 hours. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As a result, a resin (α-III) was obtained as a polysiloxane resin which is a hydrolysis-condensation product. The Mw of the resin (α-III) which is a polysiloxane resin was 5000.

Next, [A] alkali-soluble resin, [B] photoacid generator, [C] polyfunctional acrylate, and [D] chain transfer used for the preparation of the radiation sensitive resin compositions of Examples and Comparative Examples described later The agents are shown together.

<[A] alkali-soluble resin>
Resin (α-I): Copolymer (carboxyl group / epoxy group-containing alkali-soluble resin)
Resin (α-II): Polyimide precursor resin (α-III): Polysiloxane resin

<[B] Photoacid generator>
B-1: A quinonediazide compound represented by the following formula

B-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), (“IRGACURE®” from BASF) OX02 ")

<[C] polyfunctional acrylate>
C-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD (registered trademark) DPHA” by Nippon Kayaku Co., Ltd.)
C-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix (registered trademark) TO-756” manufactured by Toagosei Co., Ltd.)

<[D] Chain transfer agent>
D-1: Pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMPII-20P manufactured by Sakai Chemical Industry Co., Ltd.)

Example 1
[Preparation of positive-type radiation-sensitive resin composition]
100 parts by mass (solid content) of a copolymer solution containing a resin (α-I) and 20 parts by mass of (B-1) as a photosensitizer are mixed, and filtered through a membrane filter having a pore size of 0.2 μm. A radiation sensitive resin composition was prepared.

Example 2
[Preparation of positive-type radiation-sensitive resin composition]
100 parts by mass (solid content) of copolymer solution containing resin (α-II), C-2: 20 parts by mass of succinic acid-modified pentaerythritol triacrylate (“Aronix (registered trademark) TO-756” manufactured by Toagosei Co., Ltd.) Then, 20 parts by mass of (B-1) as a photosensitizer was mixed and filtered through a membrane filter having a pore diameter of 0.2 μm to prepare a positive type radiation sensitive resin composition.

Example 3
[Preparation of positive-type radiation-sensitive resin composition]
100 parts by mass (solid content) of a copolymer solution containing a resin (α-III), C-1: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD (registered trademark)” of Nippon Kayaku Co., Ltd. DPHA ”) and 10 parts by mass of (B-1) as a photosensitizer were mixed and filtered through a membrane filter having a pore diameter of 0.2 μm to prepare a positive radiation sensitive resin composition.

Example 4
[Preparation of negative radiation-sensitive resin composition]
100 parts by mass (solid content) of a copolymer solution containing a resin (α-I), 5 parts by mass of (B-2) as a photosensitizer, (C-1) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 100 parts by mass of a mixture (“KAYARAD (registered trademark) DPHA” manufactured by Nippon Kayaku Co., Ltd.) was mixed. A negative radiation sensitive resin composition was prepared by adding 1 part by mass of PEMPII-20P) and filtering through a membrane filter having a pore size of 0.2 μm.

Example 5
[Preparation of negative radiation-sensitive resin composition]
100 parts by mass (solid content) of a copolymer solution containing a resin (α-II), 5 parts by mass of (B-2) as a photosensitizer, C-2: succinic acid-modified pentaerythritol triacrylate (“Aronix by Toagosei Co., Ltd.”) (Registered trademark) TO-756 ") 100 parts by mass, D-1: Pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMPII-20P, manufactured by Sakai Chemical Industry Co., Ltd.) And a negative radiation sensitive resin composition was prepared by filtering through a membrane filter having a pore size of 0.2 μm.

Example 6
[Preparation of negative radiation-sensitive resin composition]
100 parts by mass (solid content) of a copolymer solution containing a resin (α-III), 5 parts by mass of (B-2) as a photosensitizer, (C-1) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 100 parts by mass of a mixture (“KAYARAD (registered trademark) DPHA” manufactured by Nippon Kayaku Co., Ltd.) was mixed, and D-1: pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd., trade name: A negative radiation sensitive resin composition was prepared by adding 1 part by mass of PEMPII-20P) and filtering through a membrane filter having a pore size of 0.2 μm.

<Evaluation of cured film>
Next, using the radiation-sensitive resin compositions prepared in Examples 1 to 6, cured films were formed as follows, and the characteristics were evaluated.

Example 7
(Evaluation of patterning properties)
The radiation sensitive resin compositions prepared in Examples 1 to 6 were applied on a glass substrate (“Corning (registered trademark) 7059” (manufactured by Corning)) using a spinner, and then on a hot plate. A coating film was formed by prebaking at 90 ° C. for 2 minutes.

Next, the obtained coating film on the glass substrate was passed through a mask having a line / space pattern with a width of 20 μm using a PLA (registered trademark) -501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Exposure was performed. Thereafter, development was performed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 25 ° C. for 60 seconds. Subsequently, running water was washed with ultrapure water for 1 minute to form a patterned cured film. Using a stylus type film thickness measuring device (α step), the thickness of each formed cured film was measured and confirmed to be in the range of 0.3 μm to 0.5 μm.

The end portions of each patterned cured film, that is, each pattern, were observed with an optical microscope, and when there was no development residue and the line pattern was formed in a straight line, it was judged that the patterning property was good. It was confirmed that the pattern formed from the radiation-sensitive resin compositions prepared in Examples 1 to 6 had no residue and a pattern having a height in the range of 0.3 μm to 0.5 μm was formed. .

Example 8
(Confirm pattern shape)
The shape of each pattern obtained in Example 7 was observed with a scanning electron microscope (SEM). In either case, it was confirmed that the shape was a forward taper. A reverse taper shape having a wide pattern upper part and a narrow lower part was not confirmed. It can be judged that the shape of the pattern formed from the radiation-sensitive resin composition prepared in Examples 1 to 6 is good.

Example 9
(Evaluation of transmittance)
The radiation-sensitive resin compositions prepared in Examples 1 to 6 were applied to a glass substrate (“Corning (registered trademark) 7059” (manufactured by Corning)) using a spinner, and then applied on a hot plate. A coating film was formed by prebaking at 2 ° C. for 2 minutes. Next, irradiation (exposure) was performed using a PLA (registered trademark) -501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and development was performed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. went. After drying, the glass substrate on which the cured film was formed was measured for light transmittance in a wavelength range of 400 nm to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.) For each glass substrate, the minimum value of light transmittance in the wavelength range of 400 nm to 800 nm was evaluated. Then, the light transmittance at a wavelength of 400 nm was used as a reference for evaluation, and when the light transmittance at a wavelength of 400 nm was 85% or more, it was determined that the light transmittance characteristics were particularly good.
The cured films obtained using the radiation-sensitive resin compositions prepared in Examples 1 to 6 all have a light transmittance of 90% or more at a wavelength of 400 nm, and the light transmittance characteristics are particularly good. there were.

Example 10
(Evaluation of voltage holding ratio)
The radiation-sensitive resin compositions prepared in Examples 1 to 6 were spin-coated on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface and ITO electrodes were deposited in a predetermined shape. After coating, prebaking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm.
Next, the coating film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. The coating film was cured to form a cured film.

Next, the substrate on which the cured film is formed on the ITO electrode and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608. (Product name) was injected to produce a liquid crystal cell.

Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system “VHR-1A type” (trade name) manufactured by Toyo Corporation. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal alignment cannot be sufficiently maintained. There is a high risk of “burn-in” such as afterimages.

All of the liquid crystal cells having cured films formed using the radiation-sensitive resin compositions prepared in Examples 1 to 6 have a voltage holding ratio of 90% or more and a good voltage holding ratio. Was confirmed. That is, it was found that the cured films formed using the radiation-sensitive resin compositions prepared in Examples 1 to 6 can provide liquid crystal display elements having an excellent voltage holding ratio.

From the above evaluation results, it can be seen that the cured films produced using the radiation-sensitive resin compositions prepared in Examples 1 to 6 have excellent patterning properties and good pattern shapes. It was.

In addition, the cured films produced using the radiation-sensitive resin compositions prepared in Examples 1 to 6 all showed high transmittance, and when applied to a liquid crystal display device, the voltage holding ratio was also good. I found out that

From the above, the cured film produced using the radiation-sensitive resin composition prepared in Examples 1 to 6 should be suitably used as a pattern for forming an uneven structure on the surface of the pixel electrode of the liquid crystal display element. I found out that
That is, it was found that the radiation-sensitive resin compositions prepared in Examples 1 to 6 can be suitably used for manufacturing a pattern for forming an uneven structure on the surface of a pixel electrode of a liquid crystal display element. .

The liquid crystal display element of the present invention is a VA liquid crystal display element that can be easily manufactured and suppresses deterioration in display quality. Therefore, the liquid crystal display element of the present invention is suitable for applications such as large liquid crystal televisions that require excellent image quality and reliability.

DESCRIPTION OF SYMBOLS 1 Liquid crystal display element 2 1st board | substrate 3 2nd board | substrate 4 Liquid crystal layer 5 Pixel electrode 6 Counter electrode 7, 7a Liquid crystal 10 Uneven structure 11 Pattern

Claims (7)

A liquid crystal layer; first and second substrates disposed opposite to each other so as to sandwich the liquid crystal layer; a pixel electrode provided on the liquid crystal layer side of the first substrate; And a counter electrode provided on the second substrate, and a height difference is in a range of 0.1 μm to 2.0 μm on at least one of the pixel electrode and the counter electrode on the liquid crystal layer side. A liquid crystal display element having a concavo-convex structure,
The concavo-convex structure has a pattern formed using a radiation-sensitive resin composition between at least one of the pixel electrode and the first substrate and between the counter electrode and the second substrate. A liquid crystal display element characterized by being formed. 2. The liquid crystal according to claim 1, wherein the liquid crystal layer is vertically aligned with at least one of the first and second substrates in a state where no voltage is applied between the pixel electrode and the counter electrode. Display element. 3. The liquid crystal display element according to claim 1, wherein the pattern is a stripe pattern. The radiation sensitive resin composition is
The liquid crystal display element according to any one of claims 1 to 3, further comprising [A] an alkali-soluble resin and [B] a photosensitizer. [B] The liquid crystal display element according to claim 4, wherein the photosensitive agent is at least one selected from a photo radical polymerization initiator and a photo acid generator. The concavo-convex structure is formed by forming a pattern on the first substrate using a radiation-sensitive resin composition, then depositing ITO to form the pixel electrode, and the surface of the pixel electrode on the liquid crystal layer side 6. The liquid crystal display element according to claim 1, wherein the liquid crystal display element is provided on the liquid crystal display. A radiation-sensitive resin composition, which is used for forming the concavo-convex structure of the liquid crystal display element according to any one of claims 1 to 6.

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