KR20170108837A - Substrate for display device, manufacturing method of the substrate for display device, and display device - Google Patents

Abstract

The present invention provides a substrate for a display device having a chromatic color pattern and a black color spacer with an excellent color property, provides a manufacturing method of the substrate for a display device, and provides a display device with high display quality. The substrate for a display device (1) comprises a switching active device (8), a color filter layer (13), the black color spacer (10), and an alignment layer (26). The color filter layer (13) has the chromatic color pattern formed with a chromatic color composite. The black color spacer (10) is a pillar shaped spacer and formed with a composite for forming the black color spacer containing a black color coloring. The alignment layer (26) is one of a polymer having an optical orientation group or a polymer not having the optical orientation group, and is formed by using a liquid crystal alignment material containing a first polymer initiator. A liquid crystal display device is composed as the display device from the substrate for the display device (1).

Description

TECHNICAL FIELD [0001] The present invention relates to a substrate for a display element, a method of manufacturing a substrate for a display element,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate for a display element, a method of manufacturing a substrate for a display element, and a display element, and more particularly to a display element substrate having a switching active element and a color filter on the same substrate, And a display element using the display element substrate.

BACKGROUND ART [0002] In recent years, thin, lightweight, and high display quality display devices have been demanded. For example, liquid crystal display devices have been actively developed. In a display element such as a liquid crystal display element, a color filter can be used to realize color display of a high display quality.

The colorization technique using this color filter can be used for an organic EL (Electro Luminescence) device using a white light emitting layer, and for color display of an electronic paper or the like. Further, color imaging of solid-state image pickup devices such as CCD (Charge Coupled Durace) image sensors and CMOS (Complementary Metal Oxide Semiconductor) image sensors is also possible.

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

The conventional liquid crystal display element 100 shown in Fig. 6 is a TN (Twisted Nematic) mode color liquid crystal display element of a thin film transistor (TFT) type. The liquid crystal display element 100 has a driving array substrate 101 and a color filter substrate 102 and has a structure in which they face each other with a liquid crystal layer 103 made of a TN liquid crystal therebetween.

A source electrode 105, a drain electrode 106, a gate electrode 107, and a switching active element (not shown) are formed on a transparent substrate 104 constituting the array substrate 101 on the side in contact with the liquid crystal layer 103 108 and a transparent electrode 109 constituting a pixel electrode are formed.

On the transparent substrate 111 constituting the color filter substrate 102, a minute chromatic color pattern 112 of red, green and blue and a black matrix 113 are arranged on the side in contact with the liquid crystal layer 103 . The red, green, and blue achromatic patterns 112 are arranged in a regular shape such as a lattice shape. A transparent common electrode 114 is formed on the chromatic pattern 112 and the black matrix 113.

On the surfaces of the substrate 104 and the substrate 111 that are in contact with the liquid crystal layer 103, alignment films 115 are formed, respectively. The alignment film 115 can be formed using a liquid crystal aligning agent. Uniform alignment of the liquid crystal layer 103 sandwiched between the substrate 104 and the substrate 111 can be realized by performing alignment treatment such as rubbing treatment of the alignment film 115. [

On a side of the substrate 104 constituting the array substrate 101 and the substrate 111 constituting the color filter substrate 102 opposite to the side in contact with the liquid crystal layer 103 in the liquid crystal display element 100 And a pair of polarizing plates 116 are disposed. 6, reference numeral 117 denotes a backlight irradiated from the backlight unit (not shown) serving as a light source of the liquid crystal display element 100 toward the liquid crystal layer 103. In FIG.

The distance between the substrate 104 constituting the array substrate 101 and the substrate 111 constituting the color filter substrate 102 in the conventional liquid crystal display element 100 is usually 2 μm or more and 10 μm or less, That is, 2 mu m to 10 mu m, and they are fixed to each other by a sealing material (not shown) formed at the peripheral portion.

In recent years, a technique has been developed in which columnar spacers (not shown) are provided between the substrate 104 and the substrate 111 (see, for example, Patent Document 1). The columnar spacer can be formed on the color filter substrate 102 by using a resin composition containing a photosensitive resin or the like and the substrate 104 and the substrate 111 for sandwiching the liquid crystal layer 103, To a predetermined value. Recently, a technique of forming the spacer by using a black composition containing a black coloring agent in addition to a photosensitive resin to form a black spacer and improving the display quality has been studied (see, for example, Patent Document 2 ).

In the conventional liquid crystal display device 100 having such a structure, the following method is known as a method of manufacturing the color filter substrate 102. [ For example, on a transparent substrate or on a transparent substrate on which a black matrix of a desired pattern is formed, a chromatic composition responsive to a suitable irradiation line is applied. As the chromatic color composition, a pigment-dispersed coloring and radiation-sensitive composition containing a pigment such as rust or blue coloring agent may be used.

Subsequently, after drying the coated film, the dried coating film is irradiated with radiation (hereinafter referred to as " exposure ") through a mask, and development processing is performed. Then, curing at a high temperature of about 230 deg. C is performed to obtain a fixed chromatic color pattern (see, for example, Patent Document 3 or Patent Document 4).

In recent years, display devices are required to have further improved display quality. For example, higher luminance, higher definition, higher contrast, and the like are required to improve the display quality of liquid crystal display elements .

As a method of improving the display quality of a display element such as a liquid crystal display element, the improvement of the performance of the color filter is effective.

It is said that it is effective to use a dye as a coloring agent used for forming a chromatic color pattern of a color filter in order to realize high definition and high contrast of a display element and high definition of a solid state image pickup device (for example, 5 to Patent Document 7).

However, the chromatic pattern formed by using the chromatic composition containing the dye has a problem that the reliability performance, particularly, the heat resistance is inferior to the chromatic pattern using the chromatic composition containing the pigment. Therefore, it has been said that it is difficult to use a conventional chromatic composition containing a dye when curing at a high temperature as described above is required in the production process of a chromatic color pattern.

Further, improvement of the structure of the display element is effective for improvement of the display quality of the display element. For example, with respect to the conventional liquid crystal display device, there is a problem of a low aperture ratio and a high brightness due to its improvement.

That is, in the above-described conventional TFT type liquid crystal display element 100, there is a fear of positional deviation in the step of overlapping the array substrate 101 and the color filter substrate 102. Therefore, in order to prevent the positional deviation from occurring, a method of widening the pattern width of the black matrix 113 formed on the color filter substrate 102 in the design stage is taken. In this manner, in the liquid crystal display element 100, although the position deviation margin when the substrates are overlapped with each other can be widened, the aperture ratio of the pixels is lowered. As a result, the luminance of the liquid crystal display element decreases and the display becomes dark.

Therefore, in order to improve the low aperture ratio of such a liquid crystal display element, a color filter-on-array structure in which a color filter is formed on an array substrate to form a substrate for a display element and alignment is unnecessary when overlapping each other has been developed See, for example, Patent Document 8 or Patent Document 9).

This color filter-on-array structure makes alignment unnecessary between the substrate for a display element, which is an array substrate on which a color filter is formed, and the counter substrate on which an electrode is formed on the entire surface, thereby eliminating the defective position deviation have. Further, since the alignment operation is not required, the manufacturing process can be simplified. Further, since there is no problem of positional deviation when the upper and lower substrates sandwiching the liquid crystal are overlapped with each other, the design of the pattern considering the positional deviation is not required, and the aperture ratio of the liquid crystal display element can be improved.

From the above, it can be seen that the display quality of a display element such as a liquid crystal display element can be improved by improving the color filter and further improving the device structure. More specifically, when a chromatic color pattern using a chromatic composition containing a dye can be used in a liquid crystal display element of a color filter-on-array structure, the display quality of the liquid crystal display element can be further improved.

Further, in the liquid crystal display element of the color filter-on-array structure, it is preferable that the liquid crystal display element has a structure having the aforementioned columnar spacer (hereinafter sometimes simply referred to as " spacer "). In the liquid crystal display element of the color filter-on-array structure, by providing the columnar spacer, it is possible to maintain the gap between the pair of substrates sandwiching the liquid crystal at a predetermined value and to control the thickness of the liquid crystal with high precision, It is possible to improve the display quality of one layer.

Further, in the liquid crystal display element, if a black spacer formed of a black composition containing a black coloring agent can be used as a spacer, the contrast ratio of the display can be improved and the display quality can be further improved.

Japanese Laid-Open Patent Publication No. 11-344700 Japanese Laid-Open Patent Publication No. 2015-135476 Japanese Unexamined Patent Application Publication No. 2-144502 Japanese Unexamined Patent Publication No. 3-53201 Japanese Patent Application Laid-Open No. 2005-99584 Japanese Patent Application Laid-Open No. 2007-219466 Japanese Patent Application Laid-Open No. 2007-316179 Japanese Patent Application Laid-Open No. 2002-357828 Japanese Patent Application Laid-Open No. 2008-146004

However, in the case of a liquid crystal display element of a color filter-on-array structure, when a dye is used as a coloring agent for a color filter, heat resistance of the dye is insufficient, and therefore it is difficult to form a high temperature curing step in the production process.

Therefore, when the columnar spacer is formed by using the resin composition, sufficient curing of the spacer can not be realized, and a desired high reliability spacer may not be formed.

Particularly, in the case of the above-mentioned black spacer, it is a low light transmittance. Therefore, sufficient curing in the exposure process is difficult, and a heat curing process is often required after the exposure process. In such a case, when a dye is used for the coloring agent of the color filter, the heat resistance of the dye is insufficient, so that heat curing at a high temperature can not be performed. As a result, a desired high reliability black spacer may not be formed.

As described above, there is provided a display element substrate which has a chromatic pattern formed of a chromatic composition containing a switching active element and a coloring agent containing a dye, further has a columnar black spacer and realizes high reliability Is strongly required. In addition, it is strongly desired to provide a display element having a high display quality such as a liquid crystal display element having the substrate for a display element and having a color filter-on-array structure.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a substrate for a display device having a switching active element, a chromatic pattern and a columnar black spacer, a highly reliable display device, and a method of manufacturing a substrate for a display device, And a display element having a high display quality.

As a result of intensive investigations, the inventors of the present invention have found that, in a substrate for a display device on which a switching active element is formed, a chromatic color pattern is formed using a chromatic composition, a black spacer is formed, and further, a liquid crystal aligning agent containing a polymerization initiator Is used to form an alignment film, the above problems can be solved.

A first aspect of the present invention is a substrate for a display element having a switching active element, a chromatic pattern, a black spacer, and an alignment film,

Wherein the black spacer comprises a black colorant,

Wherein the alignment film is formed of a liquid crystal aligning agent containing a first polymerization initiator.

In the first aspect of the present invention, the first polymerization initiator is preferably at least one selected from the group consisting of a photo-radical generator, a photo-acid generator, a photo-base generator, a thermal acid generator and a heat radical generator Do.

In the first aspect of the present invention, it is preferable that the alignment film is formed of any one of the polymer having a photo aligning group and the polymer having no photo aligning group, and the liquid crystal aligning agent containing the first polymerization initiator.

In the first aspect of the present invention, it is preferable that the black spacer has an OD (Optical Density) value of 0.3 to 4 per 1 m of the film thickness.

In the first aspect of the present invention, it is preferable that the black colorant contains at least one kind selected from the group consisting of a compound represented by the following formula (B-1), perylene black and carbon black.

(In the formula (B-1), X represents a double bond, and each of the geometric isomers is independently E or Z form, and each R ^a independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, R ^b represents a hydrogen atom, a methyl group, or a phenyl group, and R ^c represents, independently of each other, a hydrogen atom, a methyl group, or a chlorine atom)

In the first aspect of the present invention, it is preferable that the black spacer is formed of a black composition containing a colorant containing a black colorant, a first alkali-soluble resin, and a second polymerization initiator.

In the first aspect of the present invention, the black spacer is formed of a black composition containing a colorant containing a black colorant, a first alkali-soluble resin and a second polymerization initiator, and the second polymerization initiator is O -Acyloxime compounds.

In the first aspect of the present invention, it is preferable that the chromatic pattern includes a dye.

In the first aspect of the present invention, the chromatic pattern includes a dye, and the dye is selected from the group consisting of azo dyes, triarylmethane dyes, anthraquinone dyes, xanthene dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, It is preferably at least one member selected from the group consisting of lomentene dyes, cyanine dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes and quinone imine dyes.

In the first aspect of the present invention, it is preferable that the chromatic pattern is formed of a chromatic composition containing a colorant, a second alkali-soluble resin, a polymerizable compound, and a third polymerization initiator.

A second aspect of the present invention is a method for manufacturing a substrate for a display element having a chromatic pattern, a black spacer and an alignment film,

And at least the following steps [1] to [5].

[1] A process for forming a coating film of a chromatic color composition on a substrate,

[2] a step of curing the coating film of the chromatic color composition to form a colored pattern,

[3] A process for forming a coating film of a black composition on a substrate having a chromatic pattern,

[4] a step of curing the coating film of the black composition to form a black spacer,

[5] A process for forming an alignment film on a substrate on which the black spacer is formed.

A third aspect of the present invention relates to a display element having a display element substrate according to the first aspect of the present invention.

According to the present invention, there is provided a method of manufacturing a substrate for a display device, in which a substrate for a display device with high reliability is provided, and a substrate for a display device with high reliability is produced.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a main part structure of a display element substrate according to a first embodiment of the present invention. Fig.
2 is a schematic electrode wiring diagram of a display element substrate according to the first embodiment of the present invention.
3 is a schematic cross-sectional view showing a main part structure of another example of the substrate for a display element according to the first embodiment of the present invention.
4 is a schematic cross-sectional view of a liquid crystal display element according to a second embodiment of the present invention.
5 is a schematic cross-sectional view of another example of the liquid crystal display element according to the second embodiment of the present invention.
6 is a cross-sectional view schematically showing the structure of a conventional liquid crystal display element.

(Mode for carrying out the invention)

Embodiments of the present invention will be described below.

In the present invention, the term " radiation " irradiated at the time of exposure is a concept including visible light, ultraviolet light, far ultraviolet ray, X-ray, charged particle ray and the like.

Embodiment 1

≪ Substrate for display element &

The substrate for a display element according to the first embodiment of the present invention has a switching active element, a chromatic pattern, a black spacer, and an alignment film, and can be used for the constitution of a display element. In the substrate for a display element according to the first embodiment of the present invention, the chromatic pattern, the black spacer and the alignment film constitute a color filter.

In the display element substrate according to the first embodiment of the present invention, it is also possible to form a color filter by forming transparent electrodes as necessary in addition to a chromatic pattern, a black spacer and an alignment film. For example, the substrate for a display element of the present embodiment is preferably a liquid crystal display element having a color filter-on-array structure, which is capable of color display and is used for the constitution of an active-drive liquid crystal display element.

Hereinafter, the display element substrate of the present embodiment will be described with reference to the drawings.

1 is a schematic cross-sectional view showing a main part structure of a substrate for a display element according to a first embodiment of the present invention.

2 is a schematic electrode wiring diagram of a display element substrate according to a first embodiment of the present invention.

The display element substrate 1 shown in Fig. 1 is an example of the display element substrate of the present embodiment. A substrate 1 for a display element is provided with a source electrode 5, a drain electrode 6, a gate electrode 7, a switching active element 8, (R), green (G), and blue (B) color chromatic patterns 12 are arranged. The chromatic pattern 12 of each color constitutes a color filter layer 13.

That is, the layer formed by arranging the chromatic patterns of the respective colors is referred to as a color filter layer. Further, in the present invention, the color filter layer may include an insulating film formed so as to cover the chromatic pattern of each color, as described later. On the chromatic pattern 12, a transparent electrode 9 is disposed. On the transparent electrode 9, a columnar black spacer 10 is installed at a position corresponding to the upper side of the switching active element 8.

The concave structure formed in the chromatic pattern 12 of the color filter layer 13 is the contact hole 17 and the transparent electrode 9 and the drain electrode 6 are electrically connected to each other at this portion. 2, on the display element substrate 1, the source wiring 18 and the gate wiring 19 are formed in a matrix shape. A switching active element 8 is formed in the vicinity of the intersection of the source wiring 18 and the gate wiring 19. The source electrode 5 is connected to the source wiring 18, (19). In this manner, each pixel partitioned on the substrate for a display element 1 is constituted.

The color of the chromatic pattern 12 is not limited to the three colors R, G, and B, but may be a different color, or a four-color chromatic pattern by adding yellow (Y) to three RGB colors. Then, the chromatic color patterns 12 of the respective colors are arranged to form the color filter layer 13 of the display element substrate 1 as described above.

In the display device substrate 1 of the present embodiment, after the black spacer 10 is formed, an alignment film 26 that can be used for liquid crystal alignment is formed. That is, the display element substrate 1 is configured to include the alignment film 26 in addition to the switching active element 8, the color filter layer 13 including the chromatic pattern 12, and the black spacer 10. The color filter layer 13 including the chromatic pattern 12, the black spacer 10 and the alignment film 26 are formed by the color filter 15 of the display element substrate 1 together with the transparent electrode 9 .

As described later, in the display element substrate 1 of the present embodiment, the chromatic color pattern 12 constituting the color filter layer 13 is formed on the substrate 4 in the third embodiment of the present invention Is applied, patterned, and then cured. The substrate 4 is a substrate on which an electrode such as a source electrode 5 and a switching active element 8 are formed.

The chromatic color composition of the third embodiment of the present invention comprises a colorant, a second alkali-soluble resin, a polymerizable compound, and a third polymerization initiator as described later. The colorant that is a component of the chromatic color composition of the third embodiment of the present invention may include a dye. Therefore, the chromatic color pattern 12 constituting the color filter layer 13 can be formed using a dye.

The black spacer 10 can be formed by applying the composition for forming a black spacer according to the fourth embodiment of the present invention, performing patterning, and then performing curing.

The formed black spacer 10 preferably has an OD value of 0.3 to 4, that is, 0.3 to 4, per 1 mu m of thickness. Here, the OD (Optical Density) value means an optical density, and is a parameter that can be used to evaluate the light shielding ability. The larger the OD value per 1 μm of the film thickness, the higher the light shielding property of the black spacer 10 is.

The black spacer 10 having an OD value of 0.3 to 4 per 1 mu m of film thickness has excellent light shielding properties. Therefore, the black spacer 10 having an OD value of 0.3 to 4 per 1 mu m of thickness is applied to the display element substrate 1 of the present embodiment, so that the display device having the display element substrate 1 And can contribute effectively to dignification.

The alignment film 26 can be formed using any of the polymer having photo aligning group and the polymer having no photo aligning group and the liquid crystal aligning agent of the fifth embodiment of the present invention containing the first polymerization initiator. That is, the alignment film 26 can be formed by forming a coating film of the liquid crystal aligning agent of the fifth embodiment of the present invention, and performing exposure or heating as required.

The display element substrate 1 of the present embodiment having the above structure can be suitably used for the configuration of the liquid crystal display element of the color filter on array structure. Therefore, the display element substrate 1 of the present embodiment can realize high brightness and high contrast, and can be used in the construction of liquid crystal display elements of high display quality. In other words, the display element substrate 1 of the present embodiment can be used for the constitution of the liquid crystal display element of the second embodiment of the present invention with a high display quality described later.

In addition, in the substrate 1 for a display device of the present embodiment, a liquid crystal aligning agent for forming an alignment film, a polymer having a photo-aligning group, and a polymer having no photo-aligning group, as well as a first polymerization initiator .

Therefore, in forming the coating film of the liquid crystal aligning agent for forming the alignment film 26 after the black spacer 10 is formed, a part of the first polymerization initiator contained in the liquid crystal aligning agent is contained in the black spacer 10, To the inside thereof.

As a result, it is considered that when the photopolymerization initiator is used as the first polymerization initiator, the black spacer 10 can be further cured by the light when the coating film of the liquid crystal aligning agent is exposed. Further, when a thermal polymerization initiator is used as the first polymerization initiator, it is considered that the hardening of the black spacer 10 can be further promoted when the coating film of the liquid crystal aligning agent is heat-treated.

That is, it is considered that the black spacer 10 can be sufficiently cured by the action of the first polymerization initiator contained in the liquid crystal aligning agent.

Therefore, the display element substrate 1 of the present embodiment is excellent in the reliability performance and can be used in the construction of a liquid crystal display element of high reliability. In other words, the display element substrate 1 of the present embodiment can be used for the configuration of the liquid crystal display element of the second embodiment of the invention which is highly reliable, which will be described later.

3 is a schematic cross-sectional view showing a main part structure of another example of the substrate for a display element according to the first embodiment of the present invention.

The display element substrate 31 shown in Fig. 3 is a display element substrate which is an example different from the above-described display element substrate 1 of the first embodiment of the present invention. Therefore, the constituent elements common to the above-described display element substrate 1 are denoted by the same reference numerals, and redundant explanations are omitted.

The substrate 31 for a display element has an insulating film 33 on a chromatic pattern 32. Therefore, the color filter layer 34 is composed of the chromatic color pattern 32 and the insulating film 33. That is, the display element substrate 31 has a switching active element 8 on the substrate 4, and a color filter layer 34 composed of a chromatic pattern 32 and an insulating film 33. The transparent electrode 9 is disposed on the insulating film 33 of the color filter layer 34 and the black spacer 10 is set up on the transparent electrode 9.

In the display device substrate 31 of the present embodiment, after the black spacer 10 is formed, a liquid crystal alignment film that can be used for alignment of liquid crystals using the liquid crystal aligning agent of the fifth embodiment of the present invention, That is, the alignment film 26 is formed. That is, the display element substrate 31 has the color filter layer 34 composed of the switching active element 8, the colored pattern 32 and the insulating film 33, the black spacer 10, and the alignment film 26 . The color filter layer 34, the black spacer 10 and the alignment film 26 together with the transparent electrode 9 constitute the color filter 35 of the substrate 31 for a display device.

The chromatic color pattern 32 of the substrate 31 for a display element is formed by using the chromatic color composition of the third embodiment of the present invention in the same manner as the chromatic color pattern 12 of the above- And is formed by the same method.

The insulating film 33 is formed to protect the chromatic pattern 32 and to form the transparent electrode 9 having excellent characteristics on the one hand. The insulating film 33 is formed using a composition for forming an insulating film as described later. The radiation-sensitive resin composition (second radiation-sensitive resin composition) for forming an insulating film described in JP-A-2013-015795 can be used as the composition for forming an insulating film. The insulating film 33 is formed by applying and patterning the composition for forming an insulating film and then curing the same in the same manner as the chromatic color pattern 32.

The display device substrate 31 having the above structure can be suitably used for the configuration of the liquid crystal display device of the color filter on array structure similarly to the display device substrate 1 described above. Therefore, the substrate 31 for a display element can realize high brightness and high contrast, and can be used in the construction of a liquid crystal display element of high display quality. In other words, the display element substrate 31 can be used in the configuration of the liquid crystal display element of the second embodiment of the present invention with a high display quality described later.

In the display element substrate 31, similarly to the above-described display element substrate 1, an alignment film 26 is formed using the liquid crystal aligning agent of the fifth embodiment of the present invention. Therefore, the display-element substrate 31 of the present embodiment is excellent in the reliability performance and can be used for the construction of a highly reliable liquid-crystal display element, like the display-element substrate 1 described above. In other words, the display element substrate 31 of the present embodiment can be used for the configuration of a liquid crystal display element of the second embodiment of the present invention which is highly reliable, which will be described later.

Embodiment 2 Fig.

<Liquid crystal display element>

The liquid crystal display element according to the second embodiment of the present invention is a display element constructed using liquid crystal. The liquid crystal display element of the present embodiment can be a thin film transistor type which can be a color liquid crystal display element of a color filter on array structure and can be actively driven with the display element substrate of the first embodiment of the present invention have.

The liquid crystal display element of the present embodiment has the substrate for a display element according to the first embodiment of the present invention and the other substrate on which the transparent electrode is formed, on which the switching active element, the electrode, the chromatic pattern, the black spacer, Layer structure. Hereinafter, the liquid crystal display element of the present embodiment will be described with reference to the drawings.

4 is a schematic cross-sectional view of a liquid crystal display element according to a second embodiment of the present invention.

The liquid crystal display element 21 shown in Fig. 4 is an example of the liquid crystal display element of the present embodiment.

4, the liquid crystal display element 21 is, for example, a TN (Twisted Nematic) mode liquid crystal display element of the thin film transistor type and includes the substrate 1 for display element 1 of the first embodiment of the present invention And the counter substrate 22 are opposed to each other through the liquid crystal layer 23 made of TN liquid crystal. That is, the liquid crystal display element 21 has the above-described display element substrate 1 of the first embodiment of the present invention shown in Fig. 1, and common elements are used for common elements, And the description thereof will be omitted.

4, the display element substrate 1 is provided with a source electrode 5, a drain electrode 6 and a gate electrode 7 on the surface of the transparent substrate 4 on the liquid crystal layer 23 side A switching active element 8 and chromatic patterns 12 of red (R), green (G) and blue (B) colors are arranged. The chromatic pattern 12 can be formed using the chromatic color composition of the third embodiment of the present invention to be described later, and may contain a dye as a coloring agent. The chromatic pattern 12 of each color constitutes a color filter layer 13. [

On the chromatic pattern 12, a transparent electrode 9 is formed. The black spacer 10 is set up on the transparent electrode 9 so as to maintain the thickness of the liquid crystal layer 23 at a desired value by maintaining the interval between the display element substrate 1 and the counter substrate 22 .

On the other hand, on the counter substrate 22, a transparent common electrode 25 is formed on the surface of the transparent substrate 24 on the liquid crystal layer 23 side.

On the surfaces of the display element substrate 1 and the counter substrate 22 which face the liquid crystal layer 23, an alignment film 26 for liquid crystal alignment is formed. The alignment film 26 can be formed using the liquid crystal aligning agent of the fifth embodiment of the present invention as described above.

The orientation film 26 is subjected to alignment treatment such as rubbing treatment if necessary to form a uniform liquid crystal layer 23 sandwiched between the display element substrate 1 and the counter substrate 22 Thereby achieving one orientation. In the display element substrate 1 of the liquid crystal display element 21, the color filter layer 13, the black spacer 10 and the alignment film 26 including the chromatic pattern 12 are formed on the transparent electrode 9, And a color filter 15 are formed.

The distance between the display element substrate 1 and the counter substrate 22 opposed to each other through the liquid crystal layer 23 in the liquid crystal display element 21 is set to be larger than the distance between the display element substrate 1 and the counter substrate 22, Is held by the spacer 10, and is usually 2 m to 10 m. The black spacer 10 of the display element substrate 1 has a high light shielding property as described above.

The display element substrate 1 and the counter substrate 22 are fixed to each other by a sealing material (not shown) formed at the peripheral portion. In the liquid crystal display element 21, a pair of polarizing plates 28 are arranged on the side of the display element substrate 1 and the opposite substrate 22 opposite to the side in contact with the liquid crystal layer 23 have.

4, reference numeral 27 denotes a backlight irradiated from a backlight unit (not shown) serving as a light source of the liquid crystal display element 21 toward the liquid crystal layer 23. [ As the above-mentioned backlight unit, for example, a structure having a combination of a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate can be used.

A backlight unit using a white LED as a light source may also be used. As the white LED, for example, a white LED that combines a red LED, a green LED, and a blue LED to obtain white light by mixing colors;

A white LED that combines a blue LED, a red LED, and a green phosphor to obtain white light by mixing;

A white LED that combines a blue LED, a red light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing color;

A white LED for obtaining white light by mixing blue LED and YAG-base phosphor;

A white LED that combines a blue LED, an orange light emitting phosphor and a green light emitting phosphor to obtain white light by mixing;

And a white LED that combines an ultraviolet LED, a red light-emitting fluorescent substance, a green light-emitting fluorescent substance, and a blue light-emitting fluorescent substance to produce white light by mixing color.

The liquid crystal mode of the liquid crystal display element 21 of the present embodiment may be a TN mode or a super twisted nematic (STN), an in-plane switching (IPS) mode, a vertical alignment (VA) mode or an optically compensated birefringence Of the liquid crystal display mode.

In this case, for the alignment film 26, an alignment film for realizing alignment of the liquid crystal layer optimal for each liquid crystal mode is selected. For example, when the liquid crystal display element of the present embodiment is a VA mode liquid crystal display element, a vertically aligned type orientation film is used for the orientation film. However, as described above, the liquid crystal aligning agent of the fifth embodiment of the present invention is used for forming the alignment film 26 by optimizing the contained components.

5 is a schematic cross-sectional view of another example of the liquid crystal display element according to the second embodiment of the present invention.

The liquid crystal display element 51 shown in Fig. 5 is another example of the liquid crystal display element according to the second embodiment of the present invention, and is a thin film transistor TN (Twisted Nematic) mode liquid crystal display element. In the liquid crystal display element 51, the substrate 31 for a display element and the counter substrate 22 are bonded to each other through a liquid crystal layer 23 made of a TN liquid crystal, similarly to the liquid crystal display element 21 of the present embodiment described above Facing structure. The liquid crystal display element 21 has the same structure as the liquid crystal display element 21 except that the display element substrate 31 is used instead of the display element substrate 1. [ Therefore, the constituent elements common to the above-described liquid crystal display element 21 are denoted by the same reference numerals, and redundant explanations are omitted.

The liquid crystal display element 51 has an insulating film 33 formed on the chromatic color pattern 32 of the substrate 31 for a display element. Therefore, the color filter layer 34 is formed from the chromatic color pattern 32 and the insulating film 33. [ That is, the display element substrate 31 of the liquid crystal display element 51 includes a switching element 8, a color filter layer 34 composed of a chromatic pattern 32 and an insulating film 33, , And a black spacer (10).

In the liquid crystal display element 51, the transparent electrode 9 is disposed on the insulating film 33 of the color filter layer 34 composed of the chromatic color pattern 32 and the insulating film 33. On the transparent electrode 9, a black spacer 10 is installed upright. The chromatic pattern 32 can be formed using a chromatic color composition which is a third embodiment of the present invention to be described later, and can contain a dye as a colorant. The insulating film 33 is formed to protect the chromatic pattern 32 and to form the transparent electrode 9 having excellent characteristics.

The black spacer 10 defines the distance between the opposing substrate 31 and the opposing substrate 22 through the liquid crystal layer 23 and the thickness of the liquid crystal layer 23 is maintained at a desired value . The black spacer 10 has a high light shielding property as described above. In the display element substrate 31 of the liquid crystal display element 51, the color filter layer 34, the black spacer 10, and the alignment film 26, which are composed of the chromatic pattern 32 and the insulating film 33, Together with the electrodes 9, constitute a color filter 35. [

As described above, in the liquid crystal display elements 21 and 51 of the present embodiment, the display element substrates 1 and 31 including the switching active element 8 are configured to include the chromatic color patterns 12 and 32 By having color filters 15 and 35, it has a color filter on array structure. Therefore, the liquid crystal display elements 21 and 51 of the present embodiment can realize high brightness and high contrast, and can have excellent display quality.

The liquid crystal display elements 21 and 51 of the present embodiment are formed by using the liquid crystal aligning agent of the fifth embodiment of the present invention in the orientation film 26 of the display element substrates 1 and 31. Therefore, in the liquid crystal display elements 21 and 51 of this embodiment, the black spacer 10 of the display element substrates 1 and 31 is sufficiently cured, and the reliability performance is excellent.

Embodiment 3:

&Lt;

The chromatic color composition according to the third embodiment of the present invention can be used for forming the chromatic color pattern of the color filter layer of the liquid crystal display element of the display element substrate and the display element substrate of the first embodiment of the present invention.

The chromatic color composition of the third embodiment of the present invention contains a colorant, a second alkali-soluble resin, a polymerizable compound, and a third polymerization initiator. Further, other optional components may be contained as long as the effect of the present invention is not impaired. Hereinafter, each component contained in the chromatic color composition will be described.

(coloring agent)

The chromatic color composition of the third embodiment of the present invention contains a colorant, but as the colorant, a colorant containing a dye is preferable.

Examples of the above-mentioned dyes include azo dyes, triarylmethane dyes, diarylmethane dyes, anthraquinone dyes, xanthene dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, porphyrine dyes, Dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinone imine dyes, and cyanoacrylate ester dyes. Examples of the azo dye include pyridone azo dyes, pyrazolone azo dyes, and diazo dyes. Of these, azo dyes, triarylmethane dyes, anthraquinone dyes, xanthene dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, methine dyes, dipyrromethene dyes, cyanine dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes and Quinone imine dyes, and is preferably at least one selected from the group consisting of azo dyes, triarylmethane dyes, anthraquinone dyes, dyestuff dyes, phthalocyanine dyes, dipyrromethene dyes, cyanine dyes and quinophthalone dyes Is preferable to at least one selected paper.

The chromatic color composition of the present embodiment may also contain a pigment as a coloring agent. Examples of such pigments include organic pigments and inorganic pigments described in paragraphs [0012] to [0017] of JP-A No. 2009-175288. As the pigment, for example, a lake pigment as described in paragraph [0021] of Japanese Laid-Open Patent Publication No. 2013-218207 may be used.

Among them, the color index (C.I.) name, the C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, C.I. Pigment Blue 79, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. Pigment Violet 19, C.I. Pigment Violet 23 can be mentioned as a preferable pigment. In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of Japanese Laid-Open Patent Publication No. 2011-523433 may be used as a red pigment.

When a pigment is used in the chromatic color composition of the present embodiment, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. The pigment may be used by modifying its particle surface with a resin, if desired.

Examples of the resin for modifying the particle surface of the pigment include the vehicle resin described in JP 2001-108817 A, or a resin for dispersing various pigments commercially available. As the resin coating method for the surface of carbon black, for example, the methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be adopted . The organic pigment may be used by finely grinding primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. 08-179111 can be adopted.

When a pigment is used as the other coloring agent in the chromatic color composition of the present embodiment, a known dispersing agent and a dispersing aid may be further contained. Examples of known dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester Based dispersing agent, an acrylic-based dispersing agent and the like, and as a dispersing aid, a pigment derivative and the like.

Such a dispersant is commercially available, for example, a dispersant described in paragraph [0020] of Japanese Laid-Open Patent Publication No. 2014-139312 can be used.

Specific examples of the above-mentioned pigment derivatives include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

In the chromatic color composition of this embodiment, the colorant may be used alone or in combination of two or more.

In the chromatic composition of the present embodiment, the content of the colorant is preferably 5% by mass to 70% by mass, more preferably 10% by mass, and more preferably 10% by mass, in terms of forming a chromatic pattern having high solvent resistance, high brightness and high color purity. Mass% to 60 mass%. Here, the solid content is a component other than the solvent described later.

(Second alkali-soluble resin)

The second alkali-soluble resin in the chromatic color composition according to the third embodiment of the present invention is a resin having alkali developability and also functions as a so-called binder resin.

The second alkali-soluble resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a &quot; carboxyl group-containing polymer &quot;) is preferable, and an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as &quot; unsaturated monomer (b1) And another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as &quot; unsaturated monomer (b2) &quot;).

Examples of the unsaturated monomer (b1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono p-vinylbenzoic acid and the like. These unsaturated monomers (b1) may be used alone or in admixture of two or more.

Examples of the unsaturated monomer (b2) include N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Styrene, p-vinylbenzyl glycidyl ether and acenaphthylene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2- (Meth) acrylate of polyethylene glycol (polymerization degree: 2 to 10), methyl ether (meth) acrylate of polypropylene glycol (polymerization degree: 2 to 10) (Meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) ) Acrylate, 3,4-epoxy (Meth) acrylate esters such as cyclohexylmethyl (meth) acrylate, 3 - [(meth) acryloyloxymethyl] oxetane and 3- [(meth) acryloyloxymethyl] ;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Of vinyl ether;

And a macromolecule having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These unsaturated monomers (b2) may be used singly or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 mass% to 50 mass%, more preferably 10 mass% 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, the chromatic composition of the present embodiment having excellent alkali developability and storage stability can be obtained.

As specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308 Japanese Unexamined Patent Application Publication Nos. 10-300922, 11-174224, 11-258415, 2000-56118, 2004-101728, etc. Include the disclosed copolymers.

Further, in the chromatic color composition of this embodiment, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP- As disclosed in JP-A-09-325494, JP-A-11-140144, and JP-A-2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) May be used as the second alkali-soluble resin.

The second alkali-soluble resin in the present embodiment has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) To 100000, preferably 3000 to 50000.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the second alkali-soluble resin in the present embodiment is preferably 1.0 to 5.0, 3.0. Here, Mw and Mn refer to weight average molecular weight and number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The second alkali-soluble resin in the present embodiment can be produced by a known method. For example, Japanese Unexamined Patent Application Publication No. 2003-222717, Japanese Unexamined Patent Publication No. 2006-259680, International Publication No. 07 The structure, Mw, and Mw / Mn can also be controlled by a method disclosed in the publication pamphlet or the like.

In the chromatic color composition of this embodiment, the content of the second alkali-soluble resin is usually 10 parts by mass to 1000 parts by mass, preferably 20 parts by mass to 500 parts by mass, relative to 100 parts by mass of the above-mentioned colorant. By doing so, a chromatic composition having excellent alkali developability and storage stability can be obtained, and the obtained chromatic color pattern exhibits excellent chromaticity characteristics and solvent resistance.

In the chromatic color composition of this embodiment, the second alkali-soluble resin may be used singly or in a mixture of two or more kinds.

(Polymerizable compound)

The polymerizable compound in the chromatic composition of the third embodiment of the present invention is a compound which also functions as a so-called crosslinking agent.

The above-mentioned polymerizable compound is preferably a polymerizable compound having an ethylenic unsaturated bond in order to function as a crosslinking agent. Further, a compound having two or more ethylenic unsaturated groups is more preferable, and a compound having two or more (meth) acryloyl groups is more preferable.

Examples of the polymerizable compound as described above include polyfunctional (meth) acrylate which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, polyfunctional (meth) acrylate modified with caprolactone, alkylene oxide modified Polyfunctional urethane (meth) acrylate which is a reaction product of a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate, a polyfunctional urethane (meth) acrylate having a carboxyl group as a reaction product of (meth) acrylate having a hydroxyl group and an acid anhydride Polyfunctional (meth) acrylate, and the like.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol;

And tri- or higher-valent aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol, and dipentaerythritol.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate, and glycerol dimethacrylate.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.

Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, anhydride pyromellitic acid, biphenyltetracarboxylic acid dianhydride , Tetrabasic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.

Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include di (meth) acrylate modified with at least one selected from ethylene oxide of bisphenol A and propylene oxide of bisphenol A, ethylene oxide of isocyanuric acid (Meth) acrylate modified with at least one member selected from the group consisting of ethylene oxide and propylene oxide of isocyanuric acid, tri (meth) acrylate modified with at least one member selected from ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane Tri (meth) acrylate modified with at least one member selected from the group consisting of ethylene oxide of pentaerythritol, propylene oxide of pentaerythritol, ethylene oxide of pentaerythritol, and propylene oxide of pentaerythritol. Lt; RTI ID = 0.0 &gt; (Meth) acrylate modified with at least one member selected from tetra (meth) acrylate, ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol, ethylene oxide and dipentaerythritol of dipentaerythritol And hexa (meth) acrylate modified with at least one member selected from propylene oxide of lithol.

Of these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting tri- or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) (Meth) acrylate having a carboxyl group are preferable. Among the polyfunctional (meth) acrylates obtained by reacting tri- or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, di Among the polyfunctional (meth) acrylates having a carboxyl group, pentaerythritol hexaacrylate is preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride Compound is particularly preferable because it has a high intensity of a chromatic pattern and is excellent in the solvent resistance and surface smoothness of a chromatic pattern and is difficult to cause surface stains and film residue on a substrate of an unexposed portion.

In the chromatic composition of this embodiment, the polymerizable compounds may be used alone or in combination of two or more.

The content of the polymerizable compound in the chromatic composition of the present embodiment is preferably 10 parts by mass to 1000 parts by mass, particularly preferably 20 parts by mass to 500 parts by mass, relative to 100 parts by mass of the above-mentioned colorant. When the content of the polymerizable compound is within the above range, the solvent resistance can be improved.

(Third polymerization initiator)

The third polymerization initiator contained in the chromatic composition of the present embodiment is a component that generates active species capable of initiating polymerization of the above-mentioned polymerizable compound in response to radiation. Examples of such a third polymerization initiator include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, a thioxanthone compound, a triazine compound, an onium salt compound, a benzoin compound, a benzophenone compound, , Polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, onium salt compounds, and the like.

These compounds may be used singly or in combination of two or more kinds. Among them, at least one member selected from the group consisting of O-acyloxime compounds, acetophenone compounds and imidazole compounds is preferable.

Examples of the above-mentioned O-acyloxime compound include compounds described in paragraph [0094] of Japanese Laid-Open Patent Publication No. 2014-58672, among which 1,2-octanedione 1- [4- (phenyl (O-benzoyloxime)], ethanone- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- , 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime), ethanone- Methoxybenzoyl} -9H-carbazol-3-yl] -1- (O) -2-methyl- -Acetyloxime) is preferred.

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

Examples of the aforementioned? -Amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, .

Hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2- Methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl phenyl ketone.

Of these,? -Aminoketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one is more preferable Do.

Examples of the aforementioned imidazole compound include compounds described in paragraph [0081] of Japanese Laid-Open Patent Publication No. 2014-58672, among which 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl- , 2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Among them, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is more preferable.

The content of the third polymerization initiator is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass to 30 parts by mass, per 100 parts by mass of the second alkali-soluble resin. By setting the ratio of the third polymerization initiator to 1 part by mass to 40 parts by mass, the chromatic color composition of the present embodiment can form a chromatic pattern and a color filter layer having high solvent resistance even at a low exposure dose.

(menstruum)

The chromatic color composition according to the third embodiment of the present invention contains essential components such as the above-mentioned coloring agents and optionally other optional components, but is usually formulated as a liquid composition by mixing a solvent. The solvent may be appropriately selected and used as long as it does not disperse or dissolve essential components such as a coloring agent constituting the chromatic color composition and other optional components and does not react with these components and has appropriate volatility.

Examples of such a solvent include the compounds described in paragraphs [0098] to [0100] of JP-A No. 2014-58672. Among them, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-ethylhexanone, and the like are preferable from the viewpoints of solubility, pigment dispersibility, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol di Acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate.

In the chromatic color composition of this embodiment, the solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but it is preferable that the total concentration of each component except for the solvent of the chromatic composition is 5% by mass to 50% by mass, and the amount of 10% by mass to 40% desirable. By such an embodiment, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a chromatic color composition having good coatability and stability.

(Other optional components)

The chromatic color composition of the third embodiment of the present invention may optionally contain other optional components as an additive.

Examples of other optional components include fillers such as glass and alumina;

High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate);

Surfactants such as fluorine-based surfactants and silicone-based surfactants;

Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters;

Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;

An anti-aggregation agent such as sodium polyacrylate;

Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like;

A developing agent such as mono [2- (meth) acryloyloxyethyl succinate], mono [2- (meth) acryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone mono (meth) .

The chromatic color composition as the third embodiment of the present invention can be prepared by an appropriate method, and examples of the preparation method thereof include those disclosed in JP-A-2008-58642 and JP-A-2010-132874 There is a way. When both the dye and the pigment are used as the colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, the dye solution is passed through the first filter, and the dye solution having passed through the first filter is separately prepared A pigment dispersion or the like, and passing the resulting colored composition through a second filter.

In addition, the dye, the essential components such as the above-mentioned second alkali-soluble resin, and other optionally used components are dissolved in a solvent, the obtained solution is passed through a first filter, and then passed through a first filter A method in which one solution is mixed with a separately prepared pigment dispersion and the resulting composition is passed through a second filter may be employed. After the dye solution is passed through the first filter, the dye solution which has passed through the first filter and the essential components such as the above-mentioned second alkali-soluble resin and other optional components to be used are mixed and dissolved , Passing the obtained solution through a second filter, further mixing the solution having passed through the second filter with a separately prepared pigment dispersion, and passing the obtained composition through a third filter.

Embodiment 4.

<Composition for forming black spacer>

The composition for forming a black spacer (hereinafter, simply referred to as &quot; black composition &quot;) which is the fourth embodiment of the present invention is a substrate for a display element according to the first embodiment of the present invention and a liquid crystal display element Of the black spacer.

The black composition of the fourth embodiment of the present invention contains a colorant containing a black colorant, a first alkali-soluble resin, and a second polymerization initiator. Further, other optional components may be contained as long as the effect of the present invention is not impaired. Hereinafter, each component contained in the black composition will be described.

(First alkali-soluble resin)

The first alkali-soluble resin in the black composition of the fourth embodiment of the present invention is a resin having alkali developability. The first alkali-soluble resin is not particularly limited as long as it is a resin having alkali developability. Concretely, there are the same epoxy acrylate resins as those exemplified as the second alkali-soluble resin contained in the above-mentioned chromatic color composition. Among them, an epoxy acrylate resin (? 1) and an epoxy acrylate resin (? 2) to be described later can be preferably used.

[Epoxy acrylate resin (? 1)]

The epoxy acrylate resin (? 1) is obtained by adding an?,? - unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety to an epoxy resin and further reacting a polybasic acid anhydride Lt; / RTI &gt;

The epoxy acrylate resin (? 1) synthesized by this reaction has no chemical structure and substantially no epoxy group and is not limited to "acrylate", but epoxy resin is a raw material and "acrylate" Therefore, in the present invention, this is referred to according to the common usage.

(O, m, p-) cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and the like are used as raw materials for obtaining the epoxy acrylate resin , A trisphenol methane type epoxy resin, an epoxy resin having a caro structure such as the fluorene skeleton shown below, and the like can be suitably used (see Japanese Patent No. 2878486). The molecular weight of the epoxy resin is a weight average molecular weight measured by GPC, usually in the range of 200 to 200000, preferably 300 to 100000.

Examples of the above-mentioned?,? - unsaturated monocarboxylic acid and?,? - unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety include the compounds described in paragraph [0036] of the specification of Japanese Patent No. 4442292 . Among them, acrylic acid and methacrylic acid are preferred as the?,? - unsaturated monocarboxylic acid, and acrylic acid is particularly preferable because of its high reactivity.

As the?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety, acrylic acid-2-maleinyloyloxyethyl and acrylic acid-2-phthaloyloxyethyl are preferable and acrylic acid-2-maleonyloxyethyl .

The addition reaction of the?,? - unsaturated monocarboxylic acid or its ester with the epoxy resin can be carried out by a known method. The amount of the?,? - unsaturated monocarboxylic acid or ester thereof for obtaining the epoxy acrylate resin (? 1) is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin as the raw material, Is in the range of 0.7 equivalents to 1.1 equivalents.

Examples of the polybasic acid anhydrides to which the α, β-unsaturated monocarboxylic acid or its ester is added in addition to the epoxy acrylate resin (α1) include polybasic acid anhydrides such as those described in Japanese Patent No. 4442292 0039] and preferable examples thereof include compounds selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Carbonic acid dianhydride, and particularly preferred compounds are anhydrous tetrahydrophthalic acid and biphenyltetracarboxylic acid dianhydride.

With respect to the addition reaction of the above-mentioned polybasic acid anhydride, a known method may be used. The addition amount of the polybasic acid anhydride preferably ranges from 10 mgKOH / g to 150 mgKOH / g in the acid value of the resulting epoxy acrylate resin, more preferably from 20 mgKOH / g to 140 mgKOH / g is more preferable. Here, in the present invention, "acid value" means the number of mg of KOH required to neutralize 1 g of non-volatile matter excluding the solvent of the dispersant solution.

[Epoxy acrylate resin (? 2)]

The epoxy acrylate resin (? 2) is an epoxy acrylate resin excluding the epoxy acrylate resin (? 1), and includes an epoxy acrylate resin of any one of the following (B-1) to .

(B-1) A polyester resin obtained by reacting a reaction product of an epoxy compound (a) represented by the following formula (1) and an unsaturated group-containing carboxylic acid (b) with a polybasic acid anhydride (d) Epoxy acrylate resin.

(B-2) A reaction product of an epoxy compound (a) represented by the following general formula (1) and / or an epoxy compound (a ') represented by the following general formula (1A) and an unsaturated group- An epoxy acrylate resin having an acid value of 10 mg-KOH / g or more, obtained by mixing with an alcohol (c) and then reacting with a polybasic acid anhydride (d).

(B-3) A reaction product of an epoxy compound (a) represented by the following general formula (1) and / or an epoxy compound (a ') represented by the following general formula (1A) with an unsaturated group- An acid value of 10 mg-KOH / g or more, obtained by reacting an acid anhydride and / or a dibasic acid anhydride with a polybasic acid anhydride (d) containing a dibasic acid anhydride.

In the above general formula (1), X represents a linking group represented by the following general formula (2a) or (2b). However, in the molecular structure, it includes at least one adamantane structure. 1 represents an integer of 2 or 3;

In formulas (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, a substituted or unsubstituted C1- An alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent.

In the formulas (2a) and (2b), * represents a bonding site with a glycidyloxy group in the general formula (1).

In the general formula (1A), X 'represents a linking group represented by the following general formula (3). However, in the molecular structure, it includes at least one adamantane structure. 1 represents an integer of 2 or 3;

In the general formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. Y represents a divalent linking group containing an adamantane structure which may have a substituent.

In the general formula (3), * represents a bonding site with a glycidyloxy group in the general formula (1A).

[Epoxy compounds (a), (a ')]

In the general formula (3), Y is preferably a linking group represented by the following general formula (4) or (5).

The above formulas (4) and (5) may have a substituent, and * represents a bonding site with the benzene ring in the formula (3).

X in the formulas (2a) and (2b) preferably has 2 to 4 adamantane structures. When the adamantane structure is 1, the resistance to developing is lowered, and the resolution tends to be poor.

In particular, the epoxy compound (a) represented by the general formula (1) is preferably represented by the following general formula (7), and the epoxy compound (a ') represented by the general formula (1A) Lt; / RTI &gt;

In the general formula (6), R ¹⁶ to R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.

In the general formula (7), R ²⁴ and R ²⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, Phenyl group.

The adamantyl group represented by the general formulas (6) and (7) may have a substituent.

The alkyl group having 1 to 12 carbon atoms represented by R ¹ to R ²⁵ in the general formulas (2a), (2b), (3), (6) and (7) is preferably an alkyl group having 1 to 10 carbon atoms .

Examples of the substituent which these alkyl groups may have include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, .

Examples of the substituent which the phenyl group of R ¹ to R ²⁵ in the general formulas (2a), (2b), (3), (6) and (7) may have) include a halogen atom, a hydroxyl group, An alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group and a nitro group.

The adamantyl group in R ¹ to R ⁴ , R ¹³ to R ¹⁵ in the general formulas (2a) and (2b), the adamantane ring in the general formula (3) , The adamantyl group in the formula (7), the R ²⁴ in the formula (7), the adamantyl group in the R ²⁵ , the adamantane ring in the formula (4) Examples of the substituent which may be present include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group and a nitro group.

In the general formula (6), R ¹⁶ to R ²³ are preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.

In the general formula (7), R ²⁴ and R ²⁵ are preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group or a phenyl group.

The molecular weight of X represented by the general formula (1) and X 'represented by the general formula (1A) is preferably 200 or more and 1000 or less. When the molecular weight of X and X 'is less than 200, the chemical resistance tends to be poor, and when it exceeds 1000, there is a possibility that the sensitivity is low.

The epoxy equivalent of the epoxy compound (a) represented by the general formula (1) and the epoxy compound (a ') represented by the general formula (1A) is preferably 210 or more, and more preferably 230 or more. The epoxy equivalent is preferably 450 or less, and more preferably 400 or less.

The epoxy compound (a) may be used alone, or two or more epoxy compounds may be used in combination. In addition, the epoxy compound (a ') may be used alone or in combination of two or more. One or more of the epoxy compounds (a) and one or two or more of the epoxy compounds (a ') may be used in combination.

The epoxy compound (a) and the epoxy compound (a ') may be commercially available or may be synthesized according to the method described in paragraphs [0093] to [0100] of Japanese Patent No. 5169422 good.

[Carbonic acid containing unsaturated group (b)]

Examples of the unsaturated group-containing unsaturated carboxylic acid (b) include unsaturated carboxylic acids having an ethylenic unsaturated group. Specific examples thereof include monocarboxylic acids having an ethylenic unsaturated group;

(Meth) acryloyloxyalkyl esters of dibasic acids;

(Meth) acrylic acid and lactones;

(Meth) acrylic acid dimer;

And a reaction product of an unsaturated hydroxyl group-containing compound and an acid anhydride. More specifically, the compound described in paragraph [0101] of the specification of Japanese Patent No. 5169422 can be mentioned. Among them, (meth) acrylic acid is preferable.

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

As a method for reacting the epoxy group and the unsaturated group-containing carboxylic acid (b) in the epoxy compound (a) and / or the epoxy compound (a ') described above, a known technique may be used.

The ratio of adding the unsaturated group-containing carboxylic acid (b) to the epoxy group of the epoxy compound (a) and / or the epoxy compound (a ') is usually 90 mol% to 100 mol%.

[Polyhydric alcohol (c)]

As the above-mentioned polyhydric alcohol (c), one or more kinds selected from among trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane and 1,2,3-propanetriol It is preferably a polyhydric alcohol.

By using the polyhydric alcohol (c), the molecular weight of the epoxy acrylate resin (? 2) can be increased, branching (branching) can be introduced into the molecule, and a balance between molecular weight and viscosity can be obtained. In addition, the introduction rate of an acid group into the molecule can be increased, and an organic binder having a balance of sensitivity and adhesion can be obtained.

The amount of the polyhydric alcohol (c) to be used is usually about 0.01 to 0.5 parts by weight, preferably about 0.02 to 0.5 parts by weight, based on the reaction product of the epoxy compound (a) and / or the epoxy compound (a ') and the unsaturated group- Weight to about 0.2 times the weight.

[Polybasic acid anhydride (d)]

As the above-mentioned polybasic acid anhydride (d), dibasic acid anhydride, tribasic acid anhydride, tetrabasic acid anhydride and the like can be used.

As the dibasic acid anhydride (dicarboxylic anhydride), tribasic acid anhydride (tricarboxylic acid anhydride) and tetrabasic acid anhydride (tetracarboxylic dianhydride) described above, known ones can be used, 0.0 &gt; [0067], &lt; / RTI &gt; These may be used singly or in combination of two or more.

Among them, preferable as the dibasic acid anhydride is tetrahydrophthalic anhydride and succinic anhydride, and as the tribasic acid anhydride, trimellitic anhydride and hexahydrotrimellitic acid are preferable, and as the tetrabasic acid anhydride, biphenyltetracarboxylic anhydride .

The lower limit of the acid value of the epoxy acrylate resin (? 2) is usually 10 mg-KOH / g or more, preferably 50 mg-KOH / g or more and the upper limit of the acid value is preferably 200 mg- Mg-KOH / g or less.

The weight average molecular weight of the epoxy acrylate resin (? 2) according to this embodiment is preferably 1500 or more, more preferably 2000 or more. Further, it is preferably 20,000 or less, more preferably 10,000 or less.

(Second polymerization initiator)

The second polymerization initiator contained in the black composition of the present embodiment is a component which generates active species capable of initiating polymerization of the polymerizable compound contained in the black composition in response to radiation. The second polymerization initiator may be the same as those exemplified as the third polymerization initiator contained in the chromatic composition.

Among them, the second polymerization initiator preferably contains an O-acyloxime compound. The O-acyloxime compounds may be used singly or in combination of two or more.

The content of the second polymerization initiator is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass to 30 parts by mass, per 100 parts by mass of the first alkali-soluble resin. By setting the content of the second polymerization initiator to 1 part by mass to 40 parts by mass, the black composition can form a black spacer having a high solvent resistance.

(Black coloring agent)

The black colorant contained in the black composition of this embodiment is a component for making the spacer formed of the black composition black.

As the black colorant, achromatic coloring materials may be used singly or in combination of two or more, or may be made black by mixing coloring materials of chromatic colors such as red, green, and blue, or may be formed of achromatic coloring materials and chromatic coloring materials It may be a mixture of ashes. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes.

As the chromatic color material described above, the same as those exemplified as the coloring agent contained in the chromatic color composition of the third embodiment, for example, the coloring materials described in paragraphs [0072] to [0073] of the specification of Japanese Patent No. 5169422 have.

Examples of the achromatic coloring material include compounds represented by the following formula (B-1), carbon black, perylene black, acetylene black, lamp black, main black, graphite, iron black, aniline black, cyanine black, have.

In the formula (B-1), X represents a double bond, and each of the geometric isomers is independently E or Z, and R ^a independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, , R ^b represents a hydrogen atom, a methyl group or a phenyl group, and R ^c represents, independently of each other, a hydrogen atom, a methyl group or a chlorine atom.

In the formula (B-1), R ^a is preferably bonded to the 6-position of the dihydroindolone ring, and R ^c is preferably bonded to the 4-position of the dihydroindolone ring.

In the compound represented by the above formula (B-1), R ^a , R ^b and R ^c are preferably hydrogen atoms.

The compound represented by the above formula (B-1) can be produced, for example, by the method described in the pamphlet of International Publication No. 2000/24736 and International Patent Publication No. 2010/081624.

Examples of the above-mentioned carbon black include commercially available products described in paragraphs [0023] to [0026] of Japanese Patent No. 4442292, for example.

The content of the black colorant may be selected in the range of usually 1% by mass to 70% by mass, based on the total solid content in the black composition. In this range, 10 mass% to 70 mass% is more preferable, and 20 mass% to 60 mass% is particularly preferable.

The black spacer formed of the black composition has an OD (Optical Density) value per 1 탆 of film thickness, usually 0.3 to 4, preferably 0.4 to 3, more preferably 0.5 to 2. Generally, when a black spacer is formed from a black composition, the higher the OD value per 1 μm of the film thickness becomes, the harder the radiation reaches the bottom of the black spacer to be formed, and the hardening of the black spacer bottom tends to become insufficient.

When the temperature is raised in the heat treatment performed after the irradiation of radiation, the hardening of the black spacer bottom proceeds. However, when the chromatic pattern contains a dye, the dye generally has a problem that the heat resistance is poor, so that the heat treatment at a high temperature is difficult.

On the other hand, in the substrate for a display device of the first embodiment of the present invention, a part of the polymerization initiator (first polymerization initiator) contained in the liquid crystal aligning agent diffuses from the surface of the black spacer bottom into the inside thereof, It is considered that the curing of the black spacer can be further promoted. Therefore, the higher the OD value per 1 mu m of the film thickness of the black spacer, the more favorably the substrate for a display device can be manufactured using the present invention.

The amount of the first alkali-soluble resin to the black coloring agent in the black composition is usually 20% by mass to 500% by mass, preferably 30% by mass to 300% by mass, more preferably 50% by mass to 200% .

Among the black colorants exemplified above, a more preferable black colorant includes a compound represented by the formula (B-1), perylene black and carbon black. Therefore, it is more preferable that the black colorant of the present embodiment contains at least one kind selected from the group consisting of the compound represented by the formula (B-1), perylene black and carbon black. By containing such a black coloring agent, the black composition can form a black spacer of high reliability realized with a desired level of blackening at a high level.

(menstruum)

The black composition according to the fourth embodiment of the present invention contains essential components such as the above-described first alkali-soluble resin and a black coloring agent, and optionally other optional components. Usually, a solvent is added to form a liquid composition It is prepared. The solvent is not particularly limited as long as it does not disperse or dissolve the essential components such as the first alkali-soluble resin and the black coloring agent constituting the black composition or other optional components and does not react with these components and has appropriate volatility You can choose to use it.

Examples of such a solvent include those exemplified as the solvents contained in the chromatic color composition of the third embodiment, and the preferable kinds of the solvents are the same as described above.

The content of the solvent is not particularly limited, but is preferably an amount such that the total concentration of each component other than the solvent of the black composition is from 5% by mass to 50% by mass, more preferably from 10% by mass to 40% desirable. By such an embodiment, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a black composition having good applicability and stability.

(Other optional components)

The black composition according to the fourth embodiment of the present invention may optionally contain other optional components as an additive.

Other optional components include those exemplified as other optional components that may be contained in the chromatic color composition of the third embodiment.

The black composition according to the fourth embodiment of the present invention can be prepared by an appropriate method.

The black colorant is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like.

The above-described dispersion treatment is preferably carried out in a system in which a black coloring agent, a solvent and a part or all of the first alkali-soluble resin are used in combination.

Next, the composition obtained by the above-mentioned dispersion treatment and the above-mentioned other components required as components of the black composition are added and mixed to obtain a homogeneous liquid composition. The black composition obtained in the liquid phase is preferably subjected to filtration treatment with a filter or the like.

Embodiment 5:

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the fifth embodiment of the present invention can be used for forming a display element substrate of the first embodiment of the present invention and an orientation film of the liquid crystal display element of the second embodiment, . The liquid crystal aligning agent of the fifth embodiment of the present invention contains a first polymerization initiator as an essential component and usually further contains a polymer having a photo aligning group or a polymer having no photo aligning group as main components, &Lt; / RTI &gt; Hereinafter, these components will be described.

(First polymerization initiator)

The liquid crystal aligning agent of the present embodiment contains a first polymerization initiator.

Examples of the first polymerization initiator include a photo-polymerization initiator such as a low-molecular photo-radical generator, a photo-acid generator, a photo-base generator, and a thermal polymerization initiator such as a thermal acid generator and a thermal radical generator. Polymers having a partial structure functioning as an initiator may also be used. That is, the liquid crystal aligning agent of the present embodiment has at least one function selected from the group consisting of a photo-radical generator, a photo acid generator, a photo-base generator, a thermal acid generator and a thermal radical generator as the first polymerization initiator &Lt; / RTI &gt; These first polymerization initiators can be appropriately selected in consideration of the step [5] in the production method of a display element substrate described later.

[Photo radical generator]

The photo radical generator is not particularly limited as long as it generates radicals by ultraviolet rays, and examples thereof include tert-butylperoxy-iso-phthalate, 2,5-dimethyl-2,5-bis (benzoyldioxy) (Tert-butyldioxy) -isopropoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl- Propyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3, (Tert-butyldioxy) valerate, cyclohexanone peroxide, 2,2 ', 5,5'-tetra (tert-butylperoxycarbonyl) Benzophenone, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4-tetra (tert-amylperoxycarbonyl) benzophenone, 3 ', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butylperoxy Butyl peroxybenzoate, and di-tert-butyl diperoxyisophthalate; organic peroxides such as 9,10-anthraquinone, 1-chloro anthraquinone, Quinones such as 2-chloroanthraquinone, octamethylanthraquinone and 1,2-benzanthraquinone, and benzoin derivatives such as benzoinmethyl, benzoin ethyl ether,? -Methylbenzoin and? -Phenylbenzoin, .

[Photo acid generator and photobase generator]

The photo acid generator and photo-base generator are not particularly limited as far as they generate an acid or a base by ultraviolet rays, and examples thereof include a triazine-based compound, an acetophenone derivative compound, a disulfone-based compound, a diazomethane- Derivative compounds, diaryl iodonium salts, triarylsulfonium salts, triarylphosphonium salts, and iron arene complexes.

More specifically, the compounds described in paragraph [0101] of International Publication No. 2014/171493 pamphlet can be mentioned.

Of these photopolymerization initiators, it is preferable to use a photo-radical generator in view of the high effect of enhancing the adhesion between the liquid crystal layer and the alignment film.

[Thermal acid generator]

Examples of the thermal acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. As specific examples, those described in paragraph [0051] and paragraph [0057] of Japanese Laid-Open Patent Publication No. 2009-215328 can be suitably used.

[Thermal Radical Generators]

Examples of the thermal radical generator include organic peroxides such as alkyl peroxides, acyl peroxides, ketone peroxides, alkyl hydroperoxides, peroxydicarbonates and sulfonyl peroxides, inorganic peroxide peroxide, azo compounds such as azonitrile, sulfinic acids, Diazo compounds, and diazo compounds.

Specific examples include cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, feloxo 2 lactate, hydrogen peroxide, potassium persulfate, ammonium persulfate Azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, 1,1'-azobis (1-cyclohexane-1-carbonitrile), dimethyl- Azobis (2-methylbutyronitrile), 2,2'-azobis (2-amidinopropane) 2 carbonate, sodium azobisisovalerate, sodium 2,2'-azobis Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl- Bis (hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2-methyl-N- 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'- And the like crude bis (2-cyano-propanol), 2,2'-azobis (2,4,4-trimethylpentane), p- toluene sulfonic acid sodium can be suitably used.

The content of the first polymerization initiator in the liquid crystal aligning agent of the present embodiment is preferably 0.01 part by mass to 50 parts by mass with respect to 100 parts by mass of all the polymer components. Among them, the amount is preferably 0.01 part by mass to 30 parts by mass, particularly preferably 0.1 parts by mass to 20 parts by mass.

(Polymer contained in the liquid crystal aligning agent)

The polymer contained in the liquid crystal aligning agent of the present embodiment functions as a liquid crystal alignment film and is used as a main skeleton such as polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, It is preferably a polymer having a skeleton composed of a polyacetal derivative, a polystyrene derivative, a poly (styrene-phenylmaleimide) derivative, a poly (meth) acrylate derivative and the like. Such a polymer includes a polymer having a photo aligning group and a polymer having no photo aligning group, and each will be described.

[Polymer Having Photo Orientation Group]

The photo-aligning group is a functional group that imparts anisotropy to the film by light irradiation. In the present embodiment, in particular, it is a group that imparts anisotropy to the film by generating at least one of a photo-isomerization reaction and a photo-dimerization reaction.

Specific examples of the photo-aligning group include azobenzene, stilbene,? -Imino-? -Ketoester, spiropyran, spirooxazine, cinnamic acid, chalcone, stilbazole, benzylidene phthalimidine, coumarin, And a group having a structure derived from at least one compound selected from the group consisting of serylene and anthracene. As the photo-alignment group described above, among these groups, a group having a structure derived from cinnamic acid is particularly preferable.

As the polymer having a photo-orientable group, it is preferable that the above-mentioned photo-orientable group is a polymer bonded directly or via a linking group. As such a polymer, for example, there may be mentioned a polymer in which at least one of the polyamic acid and the polyimide is bonded with the photo-alignment group, and a polymer different from the polyamic acid and the polyimide is bonded to the photo-orienting group.

In the latter case, examples of the basic skeleton of the polymer having a photo-orientable group include poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, polyolefin, and polyorganosiloxane.

As the polymer having the above-mentioned photo-orientable group, it is preferable that the basic skeleton is polyamic acid, polyimide or polyorganosiloxane. Among them, a polyorganosiloxane is particularly preferable and can be obtained, for example, by the method described in WO 2009/025386.

[Polymer Having No Photo Orientation Group]

As the polymer having no photo-aligning group, polyimide having no photo-aligning group can be preferably used.

The polyimide having no photo-aligning group can be obtained by dehydrating and ring-closure of a polyamic acid having no photo-aligning group to imidize it. Such a polyamic acid can be obtained, for example, by reacting a tetracarboxylic acid dianhydride with a diamine, and can be obtained as described in JP-A-2010-97188.

The above-mentioned polyimide may be a completely imidized product obtained by dehydrating and ring closure of all of the arboric acid structure of the polyamic acid which is a precursor thereof. The polyimide may be subjected to dehydration ring closure of only a part of the arboric acid structure to form a partial imide Cargo is good. The above-mentioned polyimide preferably has an imidization rate of 30% or more, more preferably 50% to 99%, and still more preferably 65% to 99%.

The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring and may be obtained, for example, as described in Japanese Patent Laid-Open Publication No. 2010-97188.

[Polymer having a partial structure functioning as a polymerization initiator]

Examples of the polymer having a partial structure functioning as a polymerization initiator include at least one partial structure selected from the group consisting of the following formulas (101) to (108), the following formulas (101-1) Hereinafter, also referred to as &quot; specific partial structure &quot;).

(Of the formulas (101) to (108)

Z each independently represent a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,

a is an integer of 0 to 4,

b is an integer of 0 to 3,

c is an integer of 0 to 5,

R ₁₀₁ , R ₁₀₂ , R ₁₀₄ , R ₁₀₅ , R ₁₀₆ , R ₁₀₇ and R ₁₀₈ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, R ₁₀₁ and R _The alkyl group, alkoxy group, aryl group, arylalkyl group, alkenyl group, alkenyloxy group, cyclic alkyl group, and heterocyclic group may have a substituent,

R ₁₀₃ represents a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a group selected from the group represented by the following formula (110).

(In the formula (110), Y ₂ represents a methylene group, -NR ₂ , an oxygen atom, a sulfur atom, each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and Z and c are as defined above ), The alkoxy group may have a substituent,

* Indicates a combined hand.)

(Of the formulas (101-1) and (101-2)

_{Z, a, R 101, R} 102, R 103 And * is as defined above, and d is an integer of 1~5, R _109, R ₁₁₀ are each independently a hydrogen atom, an alkyl group of a halogen atom, a hydroxyl group, the number of carbon atoms from 1 to 20, carbon atoms, 1 to An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms, and R ₁₀₁ And R ₁₀₂ may be connected to form a 3- to 6-membered cyclic alkane or heterocyclic group, and the alkyl group, alkoxy group, aryl group, arylalkyl group, alkenyl group, alkenyloxy group, cyclic alkyl group or heterocyclic group may have a substituent .

Provided that at least one selected from the group consisting of R ₁₀₉ and R ₁₁₀ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms.

The specific partial structure which is a partial structure functioning as a polymerization initiator will be described.

In the specific structure according to the formulas (101) to (108), the formulas (101-1) and (101-2), an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a cyclic alkyl group, The substituent may be a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

The substituent of the aryl group may be an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

Examples of the substituent of the arylalkyl group include an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an amino group, an alkylthio group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, It is also good.

The alkyl group, alkoxy group, alkenyl group and cyclic alkyl group may have a branched structure.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, Isohexyl, isohexyl, isohexyl, isohexyl, isohexyl, 2-ethylhexyl, t-octyl, nonyl, iso nonyl, decyl, isodecyl, undecyl, dodecyl, Ethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

The alkoxy group having 1 to 20 carbon atoms includes, for example, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy and the like.

Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group and a biphenylene group.

Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl,? -Methylbenzyl,?,? - dimethylbenzyl, phenylethyl and 9-fluorenylmethyl.

Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, Decenyl, and the like.

Examples of the alkenyloxy group having 2 to 12 carbon atoms include vinyloxy group, 1-propenyloxy group and the like.

Examples of the 3- to 6-membered cyclic alkane include cyclopentane rings, cyclohexane rings and the like.

Examples of the heterocyclic group include groups in which one of the carbon atoms of the cyclic alkane is substituted with a nitrogen atom.

Next, a polymer to which a partial structure functioning as a polymerization initiator binds will be described. The partial structure functioning as a polymerization initiator can be introduced as a polymer of the polymer or as a terminal group.

Examples of the polymer include polyamides, polyimides, polyamic acid esters, polyesters, polyamides, polyorganosiloxanes, cellulose derivatives, polyacetal derivatives, polystyrene derivatives, poly (styrene-phenylmaleimide) Derivatives, and the like, and polyorganosiloxane, polyamic acid, polyamic acid ester, polyimide, and polyamide are more preferable. The weight average molecular weight of such a polymer is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

The polymer having a partial structure functioning as a polymerization initiator is preferably, for example, the following polymers (i) to (f), more preferably polymers (i) to (iii) and (f).

(I) a polyorganosiloxane which is the reaction product of an epoxy group-containing polyorganosiloxane and a carbonic acid having a specific partial structure. Here, the epoxy group-containing polyorganosiloxane may be, for example, a hydrolysis-condensation product of a silane compound containing a hydrolyzable silane compound having an epoxy group.

(Ii) a polyorganosiloxane which is a hydrolytic condensate of a silane compound containing a hydrolyzable silane having a specific partial structure.

(Iii) polyamic acid which is the reaction product of tetracarboxylic acid dianhydride and a diamine having a specific partial structure.

(Iv) a polyamic acid ester which is a reaction product of the polyamic acid and the esterifying agent of (iii) above.

(V) A polyamic acid ester which is the reaction product of a tetracarboxylic acid diester and a diamine having a specific partial structure.

(Vi) a polyamic acid ester which is the reaction product of a tetracarboxylic acid diester dihalide with a diamine having a specific partial structure.

(Iii) a polyimide which is a dehydration condensate of the polyamic acid of the above (iii).

(Ⅷ) Polyamide which is the reaction product of dicarboxylic acid and diamine having a specific partial structure.

(Iii) Polyamides which are reaction products of diamines and dicarboxylic acids having a specific partial structure.

(Other components)

The liquid crystal aligning agent of the present embodiment may contain other components other than the above-mentioned components. Examples of the other components include a curing agent, a curing catalyst, a curing accelerator, a polymerization initiator, an epoxy compound, a functional silane compound, a surfactant, and a photosensitizer.

The liquid crystal aligning agent of the present embodiment may suitably contain a solvent in view of obtaining the coating film of the liquid crystal aligning agent or the intended coating film.

The content of the solvent in the liquid crystal aligning agent of the present embodiment can be appropriately selected from the viewpoint of obtaining the above-described coating method of the liquid crystal aligning agent and the intended coating film thickness. For example, the content of the solvent in the liquid crystal aligning agent is preferably 50% by mass to 99.9% by mass from the viewpoint of forming a uniform alignment film by coating.

In particular, it is preferably 60% by mass to 99% by mass, and particularly preferably 65% by mass to 99% by mass. The solvent used in the liquid crystal aligning agent is not particularly limited as long as it is a solvent for dissolving the polymer contained in the liquid crystal aligning agent, the first polymerization initiator, and optionally other components used.

Embodiment 6:

&Lt; Manufacturing Method of Substrate Substrate &

Next, a manufacturing method of a display element substrate according to a sixth embodiment of the present invention will be described.

In the production of the substrate for a display element according to the sixth embodiment of the present invention, the step of forming a chromatic color pattern from the chromatic color composition which is the third embodiment of the present invention described above, and the step of forming the chromatic color pattern, which is the fourth embodiment of the above- And a step of forming an alignment film from the liquid crystal aligning agent of the fifth embodiment of the present invention described above as main manufacturing steps. Then, a color filter constituted by the above-described color filter layer including a chromatic color pattern, a black spacer and an alignment film can be manufactured.

In addition, in the step of forming the color filter layer constituted by arranging the chromatic patterns of the respective colors, the transparent electrode can be formed on the color filter layer, and the transparent electrode can be formed with the chromatic pattern, the black spacer, Can be manufactured.

It is also possible to form a color filter layer including a chromatic pattern and an insulating film by forming an insulating film on the chromatic pattern. In this case, in addition to the above, a process for forming an insulating film is further included as a main manufacturing process. Hereinafter, a method for manufacturing a display element substrate will be described.

In the method of manufacturing a substrate for a display device of the present embodiment, it is preferable that a color filter layer including a chromatic color pattern and a black spacer are formed and include at least the following steps [1] to [5].

[1] A coating film of a chromatic color composition is formed on a substrate on which a switching active element, an electrode, etc. (source electrode, drain electrode, gate electrode, source wiring, gate wiring, etc., (Hereinafter sometimes referred to as &quot; [1] step &quot;),

[2] A process for curing a coating film of a chromatic composition obtained in the process [1] to form a chromatic pattern (hereinafter sometimes referred to as "process [2]")

[3] A process for forming a coating film of a black composition on a substrate having a chromatic color pattern obtained in the process [2] (hereinafter sometimes referred to as "process [3]")

[4] The step of curing the coating film of the black composition obtained in the step [3] to form a black spacer (hereinafter sometimes referred to as "step [4]")

[5] A process for forming an alignment film using a liquid crystal aligning agent on a substrate formed with the black spacer obtained in the process [4]

As another example, in the case of forming a color filter layer including a chromatic pattern and an insulating film by forming an insulating film on a chromatic pattern, the following process [a] is performed between the process [2] To [d] in the following order.

(a) a step of forming a coating film of a composition for forming an insulating film on the cured colored pattern on the substrate after the step [2] (hereinafter sometimes referred to as "the step [a]")

(b) a step of irradiating at least a part of the coating film of the composition for forming an insulating film formed in the step [a] (hereinafter sometimes referred to as "step [b]")

a step of developing the coating film irradiated with the radiation in the [c] [b] step (hereinafter sometimes referred to as &quot; [c] step &quot;

[d] Step of curing the developed coating film in the step [c] (hereinafter sometimes referred to as &quot; [d] step &quot;)

By the manufacturing method of the substrate for a display element according to the present embodiment including each of the above processes, the chromatic color composition can be used to form a chromatic pattern on a substrate on which a switching active element, an electrode, and the like are formed. In addition, the black spacer described above can be used to form a black spacer. Then, an alignment film can be formed on the substrate on which the black spacer is formed.

When an insulating film is formed in the color filter layer, an insulating film can be formed on the obtained chromatic color pattern by using a composition for forming an insulating film. As a result, it is possible to form a substrate for a display device having a color filter having excellent color characteristics, good heat resistance, chemical resistance, voltage preservation ratio, and the like and having high reliability.

Each step will be described in detail below.

[[1] Process]

In this step, a coating film of the above-described chromatic color composition is formed on a substrate. A switching active element, a source electrode, a drain electrode, a gate electrode, a source wiring, a gate wiring, and the like are formed on this substrate. These switching active elements and the like are formed by repeating etching on a substrate by a normal semiconductor film forming film, an insulating film forming film, and a photolithography method.

A chromatic composition containing, for example, a red dye is coated on the surface of the substrate such as a switching active element or the like, and then preliminary heating (hereinafter also referred to as "prebaking") is performed to evaporate the solvent, . As another method of forming a coating film on a substrate, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Unexamined Patent Application Publication No. 7-318723 and Japanese Unexamined Patent Publication No. 2000-310706 can be adopted.

In this method, first, a partition wall serving also as a light shielding function is formed on the surface of the substrate. Next, a chromatic composition containing, for example, a red dye or the like is ejected by an ink jet apparatus in the partition wall formed, and then pre-baked to evaporate the solvent to form a coating film.

Examples of the material of the substrate include glass such as soda lime glass and alkali-free glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, aromatic polyamide, polyamideimide, polyimide, . These substrates may be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition or the like, if desired.

Examples of the method of applying the chromatic composition on a substrate include a spray method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, and a bar coating method. Of these, the spin coating method and the slit die coating method are preferable.

The prebaking is usually carried out at 70 ° C to 110 ° C for 1 minute to 10 minutes.

The film thickness after drying (pre-baking) is usually 0.6 탆 to 8.0 탆, preferably 1.2 탆 to 5.0 탆.

Before the step [2] to be described later, a part of the coated film after drying may be removed.

For example, a coated film having a predetermined pattern can be formed by irradiating (irradiating) a dried coating film through a photomask and developing it using an alkali developing solution to dissolve and remove the unexposed portion of the coating film.

More specifically, for example, a coating film of a red colored composition is coated on a substrate, and then the substrate is processed in the order of prebaking, exposure, and development to form a substrate in which red coating film patterns are arranged in a predetermined arrangement .

The barrier rib can be formed by forming a thin metal film such as chromium film formed by sputtering or vapor deposition into a desired pattern by using a photolithography method. However, by using a curable composition containing a black coloring agent, Can be formed in the same manner as in the formation of the pattern.

Examples of the light source of radiation include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp or a low pressure mercury lamp, or a lamp light source such as argon ion laser, YAG laser, XeCl excimer laser, And a laser light source such as a laser. Radiation with a wavelength in the range of 190 nm to 450 nm is preferred. As an exposure light source, an ultraviolet LED may be used. The exposure dose of the radiation is preferably 10 J / m 2 to 10,000 J / m 2.

Examples of the alkali developing solution include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- undecene, 1,5-diazabicyclo- [4.3 0.0 &gt; 0] -5-nonene. &Lt; / RTI &gt;

A water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added in an appropriate amount to the alkali developing solution. After the alkali development, water washing is usually carried out. As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (drilling) development method, and the like can be applied. The development conditions are preferably 5 seconds to 300 seconds at room temperature.

In place of the alkali developing method, a solvent developing method may also be used. The solvent developing method can be carried out in the same manner as in the alkali developing method except that an organic solvent is used instead of the alkali developing solution in the alkali developing method. As for a more specific method, for example, Japanese Laid-Open Patent Publication No. 2014-199272 can be taken into consideration, the contents of which are incorporated herein by reference.

[[2] Process]

After forming a coating film which may have a predetermined pattern in the [1] process, the coating film is cured to form a chromatic pattern. In order to harden the coating film, usually baking (hereinafter also referred to as "post baking") is performed. The post baking temperature is, for example, 180 to 280 占 폚. The post baking time is, for example, 10 minutes to 60 minutes.

The film thickness of the chromatic color pattern formed in this way is usually 0.5 탆 to 5 탆, preferably 1.0 탆 to 3 탆.

After forming the chromatic pattern, a part of the chromatic pattern may be removed. As a method of removing a part of the chromatic pattern, an etching method can be mentioned.

In the etching method, for example, a photoresist layer is formed on a chromatic pattern obtained by curing a coating film, the photoresist layer is removed in a pattern to form a resist pattern, and the resist pattern is subjected to dry etching And by removing the resist pattern remaining after etching, a chromatic pattern having a predetermined pattern can be formed. As for a more specific method, for example, Japanese Laid-Open Patent Publication No. 2008-241744 can be considered, and the contents thereof are incorporated herein.

As described above, in step [2], a chromatic color pattern can be formed from a chromatic color composition.

Further, if necessary, a chromatic color pattern of red is formed by the process [1] and the process [2], and then each of the chromatic color compositions of green or blue is used, A green colored pattern and a blue colored pattern can be sequentially formed on the same substrate.

Accordingly, a chromatic pattern of three primary colors of red, green, and blue can be disposed on the substrate. That is, a color filter layer including a chromatic pattern of three primary colors of red, green, and blue can be formed. However, the order and the number of colors for forming the chromatic pattern of each color are not limited to those described above.

In the process [2], after forming a chromatic pattern, a transparent conductive layer made of ITO can be formed on a chromatic pattern, for example, by sputtering. Subsequently, the transparent conductive layer is etched by photolithography to form a transparent electrode on the chromatic pattern.

[3] Process

On the substrate having the chromatic color pattern obtained in the step [2], a coating film of the black composition is formed on the transparent electrode.

In the case of forming a coating film by a coating method, a coating film can be formed by applying a solution of a black composition onto a substrate having a chromatic pattern or the like formed thereon, preferably by pre-heating (prebaking) the coating surface. As a method for applying the black composition, suitable methods such as spraying, roll coating, spin coating (coating method), slit coating (slit die coating), bar coating, can do. Of these, a spin coating method or a slit coating method is preferable.

The conditions of the above-described prebaking vary depending on the kind of each component, the mixing ratio, etc., but are preferably 70 deg. C to 120 deg. C, and are about 1 minute to 15 minutes. The thickness of the coating film after pre-baking is preferably 0.5 to 10 mu m, more preferably 1.0 to 7.0 mu m.

Subsequently, in order to form a black spacer at a desired position, a part of the coating film after the preheating (prebaking) can be removed. As a method of removing a part of the coating film, for example, it is possible to irradiate a part of the coating film with a radiation through a photomask having a predetermined pattern, followed by developing the coating film.

The intensity of the irradiated radiation at a wavelength of 365 nm is preferably from 100 J / m 2 to 5,000 J / m 2, more preferably from 200 J / m 2 to 3,000 J / m &lt; 2 &gt; is more preferable.

Next, the coating film of the black composition after the irradiation with radiation is developed to remove unnecessary portions to form a black pattern having a predetermined pattern.

As the developing solution and developing method used for development, the same developing solution and developing method as those described in the [1] step may be employed.

[4] Process

After forming a coating film which may have a predetermined pattern in the process [3], a black spacer is formed by curing the coating film. In order to harden the coating film, usually, baking (post baking) is performed. The post baking temperature is, for example, 150 to 280 DEG C, but preferably 160 to 230 DEG C, more preferably 170 to 220 DEG C in consideration of the heat resistance of the dye contained in the chromatic color pattern, More preferably 180 to 210 캜. The post baking time is, for example, from 5 minutes to 180 minutes.

[5] Process

The above liquid crystal aligning agent is applied onto a transparent electrode on which a black spacer is formed by using a substrate having a chromatic pattern and a black pattern obtained after the above-mentioned [4] process, for example, by a roll coater method, a spinner method, , An ink jet method, or the like. Subsequently, the substrate coated with the liquid crystal aligning agent is pre-baked, and thereafter baked to form a coated film.

The prebaking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The prebaking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. The post-baking temperature is preferably 80 ° C to 300 ° C, more preferably 120 ° C to 250 ° C.

The post baking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 mu m to 1 mu m, more preferably 0.005 mu m to 0.5 mu m.

The solid concentration of the liquid crystal aligning agent used (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., % To 10% by mass.

When a polymer having a photo-orientable group is contained as a liquid crystal aligning agent, the above-mentioned coating film is irradiated with linearly polarized light, partially polarized radiation, or unpolarized radiation, thereby imparting liquid crystal aligning ability. Such irradiation of radiation corresponds to alignment treatment of the alignment film.

As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. Particularly, as the radiation, it is preferable to use ultraviolet rays including light having a wavelength of 300 nm to 400 nm. When the radiation to be used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction to give a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined.

The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, and more preferably 10 J / m 2 to 5,000 J / m 2.

When the polymer used in the liquid crystal aligning agent contains a polymer having no photo-aligning group, it is also possible to use a coating film after post-baking as an alignment film. If necessary, the coating film after post-baking may be subjected to a rubbing treatment (rubbing treatment) in a certain direction with a roll of cloth made of fibers such as nylon, rayon or cotton to give a liquid crystal aligning ability It is possible.

As described above, in the case where the alignment film is formed on the substrate on which the black spacer is formed, a part of the first polymerization initiator contained in the liquid crystal aligning agent in forming the coating film of the liquid crystal aligning agent after the formation of the black spacer is a black spacer Is diffused from the surface to the inside thereof.

As a result, when a thermal polymerization initiator is used as the first polymerization initiator, it is considered that the black spacer curing can be further promoted when the coating film of the liquid crystal aligning agent is heat-treated. When a photopolymerization initiator is used as the first polymerization initiator, it is considered that the black spacer can be further cured by the light when the coating film of the liquid crystal aligning agent is exposed to light.

That is, it is considered that by the action of the first polymerization initiator contained in the liquid crystal aligning agent, the black spacer can be cured more sufficiently while maintaining a high display quality of the dye which may contain a chromatic pattern.

Therefore, the color filter manufactured in the manufacturing method of the substrate for a display element of the present embodiment is excellent in the reliability performance and can be used for the constitution of the display element substrate. As a result, the display element substrate manufactured in the method for manufacturing a display element substrate of the present embodiment has excellent reliability and can be used for the construction of a highly reliable liquid crystal display element. That is, the display element substrate of the present embodiment can be used in the constitution of the liquid crystal display element of the second embodiment of the present invention described above, contributing to its high reliability.

In the case where the substrate for a display element of the present embodiment has an insulating film on a chromatic pattern, the following steps [a] to [d] are performed before the transparent electrode is formed after the step [2] .

[[a] Process]

After the step [2], a coating film of a composition for forming an insulating film is formed on the chromatic pattern on the substrate having the chromatic pattern formed thereon.

As the insulating film forming composition to be used, for example, the radiation sensitive resin composition (second radiation sensitive resin composition) for forming an insulating film described in JP-A-2013-015795 can be mentioned as described above.

Then, a coating film can be formed by applying the composition for forming an insulating film by a coating method, and then preferably by pre-baking the coated surface.

[[b] Process]

Then, at least a part of the coating film formed in the step [a] is irradiated with radiation. At this time, when irradiating only a part of the coating film, for example, it is possible to irradiate through a photomask having a predetermined pattern.

[[c] Process]

Next, the coating film after irradiation with the radiation is developed to remove unnecessary portions to form a predetermined pattern.

[[d] Process]

Subsequently, the obtained patterned coating film is cured by a suitable heating device such as a hot plate or an oven to obtain an insulating film as a cured film. In order to harden the coating film, usually, baking (post baking) is performed. The post-baking temperature is preferably, for example, 180 ° C to 280 ° C, and the post-baking time is, for example, 5 minutes to 180 minutes.

After formation of the insulating film, a transparent conductive layer made of, for example, ITO can be formed on the insulating film by sputtering or the like. Subsequently, the transparent conductive layer is etched by photolithography, and a transparent electrode can be formed on the insulating film.

According to the above manufacturing method, a color filter having an achromatic pattern and an insulating film and having excellent color characteristics, a black spacer, and an alignment film is manufactured by manufacturing a chromatic pattern and forming an insulating film thereon to form a color filter layer can do. As a display device substrate according to the first embodiment of the present invention, a highly reliable display device substrate can be manufactured.

Embodiment 7:

&Lt; Method of manufacturing substrate for PSA mode liquid crystal display element >

The display element substrate manufactured by the method for manufacturing a display element substrate according to the sixth embodiment of the present invention described above can be preferably used as a substrate for a PSA (Polymer Sustained Alignment) mode liquid crystal display element.

In the PSA mode, a polymerizable compound such as a photopolymerizable polymer is mixed in a liquid crystal material such as a liquid crystal compound constituting a liquid crystal layer, and the liquid crystal layer is sandwiched between a pair of substrates to form a liquid crystal cell After assembling, the liquid crystal cell is irradiated with light by applying a voltage between a pair of electrodes sandwiching the liquid crystal layer, thereby polymerizing the polymerizable compound to control the molecular orientation of the liquid crystal molecules in the liquid crystal layer. According to this technique, there is an advantage that the viewing angle can be increased and the response speed can be improved in the liquid crystal display element.

Hereinafter, a method of manufacturing a substrate for a PSA mode liquid crystal display element according to a seventh embodiment of the present invention will be described.

The method for producing the substrate for the PSA mode liquid crystal display element can be manufactured through a process including the following (i) to (iii).

(i) a step of applying a liquid crystal aligning agent according to the fifth embodiment of the present invention onto a transparent electrode of a pair of substrates each having a transparent electrode, and thereafter heating it to form a coating film (hereinafter referred to as " Process "in some cases)

(Ii) a step (hereinafter referred to as &quot; step (ii)) &quot; in which a pair of substrates on which a coating film is formed is opposed to the coating film through a liquid crystal layer containing a liquid crystalline compound so as to face each other )

(Iii) a step of irradiating light to the liquid crystal cell in a state in which a voltage is applied between transparent electrodes of a pair of substrates (hereinafter referred to as &quot; step (iii)

Each of these steps will be described below.

[(I) Process]

In this step, the coating film of the liquid crystal aligning agent of the fifth embodiment of the present invention is applied onto a pair of substrates each having a transparent electrode, followed by pre-baking and further post baking, Is formed.

As the pair of substrates described above, there are used a chromatic pattern and a black spacer, which are manufactured by a manufacturing process including the steps [1] to [4] of the manufacturing method of a substrate for a display device according to the sixth embodiment of the present invention described above And the other substrate on which the transparent electrode used in the structure of the liquid crystal display element of the second embodiment of the present invention described above is formed can be used.

As a result, the substrate for a display device suitable for the PSA mode liquid crystal display element can be manufactured by the present step (i).

As a method for applying the liquid crystal aligning agent, it is preferably performed by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. The conditions of pre-baking and post-baking are the same as those of the above-described [5] process of the sixth embodiment of the present invention.

The coating film thus formed may be provided as an alignment film as it is in the following step (ii), or may be provided in the step (ii) as an orientation film after rubbing treatment on the coating film surface if necessary. This rubbing treatment can be performed by rubbing the coating film surface in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon, or cotton.

[(Ii) Process]

Two liquid crystal cells are prepared by arranging two liquid crystal layers containing a liquid crystal compound and a photopolymerizable compound between two substrates arranged opposite to each other in the manner described above. For example, a vacuum injection method or an ODF (One Drop Fill) method can be used to manufacture the liquid crystal cell.

As a specific method, for example, reference can be made to paragraphs [0086] to [0088] of Japanese Laid-Open Patent Publication No. 2015-99344. The thickness of the liquid crystal layer of the liquid crystal cell to be manufactured in this way is preferably 1 to 5 mu m.

In recent years, a further high-speed response of the liquid crystal display element of the PSA mode has been investigated. As this technique, attempts have been made to introduce a monofunctional liquid crystal compound having one of an alkenyl group and a fluoroalkenyl group into a liquid crystal layer .

Examples of monofunctional liquid crystalline compounds having any one of an alkenyl group and a fluoroalkenyl group include compounds described in paragraph [0087] of Japanese Laid-Open Patent Publication No. 2015-99344 and Japanese Laid- -285499, JP-A-9-104644, and JP-A-6-108053.

[(Iii) Process]

After the liquid crystal cell is assembled by the step (ii), the liquid crystal cell is irradiated with light while a voltage is applied between the transparent electrodes of the pair of substrates. The voltage applied here may be, for example, 5V to 50V, DC or AC. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable.

As the light source of the irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet light of the above-mentioned preferable wavelength range can be obtained by a means for using the light source in combination with, for example, a filter diffraction grating or the like. The dose of light is preferably 1,000 J / m 2 or more and less than 200,000 J / m 2, and more preferably 1,000 J / m 2 to 100,000 J / m 2.

Thus, a PSA mode liquid crystal display element can be obtained. That is, the substrate for the PSA mode liquid crystal display element can be manufactured through the steps including (i) to (iii) above.

In the manufactured PSA mode liquid crystal display element, a pair of polarizing plates can be bonded to the outer surface of the liquid crystal cell after light irradiation. Examples of the polarizing plate used herein include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state, a polarizing plate sandwiched by a cellulose acetate protective film, or a polarizing plate made of H film itself.

(Example)

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

<Preparation of chromatic color composition>

Preparation Example 1

The components shown in the following Table 1 were mixed and then filtered through a Millipore filter having a pore size of 0.5 탆 to prepare a red colored composition (r-1).

Preparation examples 2 to 13

(R-2) to (r-4) and (g-1) were obtained in the same manner as in Preparation Example 1, except that the kinds of the components to be mixed were changed as shown in Table 1, ) To (g-4), (b-1) to (b-5) were prepared. (B-2) to (r-4) are red, and the chromatic compositions (g-1) to ) Is a blue composition. The values shown in Table 1 are parts by mass.

&Lt; Preparation of black composition >

Preparation Example 101

The components shown in Table 2 were mixed and then filtered through a membrane filter with a pore size of 1 占 퐉 (manufactured by Advantech Corporation) to prepare a black composition (bk-1).

Preparation examples 102 to 104

Black compositions (bk-2) to (bk-4) were prepared in the same manner as in Preparation Example 101, except that the kinds of the components to be mixed were changed as shown in Table 2 below. The values shown in Table 2 are parts by mass. The OD value of the thickness of 1.0 mu m was measured by the following method.

The OD value was obtained from the following relationship using an X-rite 361T (vial) densitometer.

OD value = log ₁₀ (I ₀ / I)

I ₀ is the incident light intensity, and I is the transmitted light intensity. Further, since the OD value is proportional to the film thickness, it is expressed as an OD value per 1.0 mu m in the present invention.

&Lt; Preparation of liquid crystal aligning agent &

Synthesis Example 1

34.8 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (hereinafter referred to as "TCA") as tetracarboxylic dianhydride, 15.6 g of 3- (2,4-diaminophenoxy) cholestane as a diamine, 12.6 g of 3,5-diaminobenzoic acid and 12.6 g of 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden- -Pyrrolidone (NMP), and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. The solution viscosity measured by taking a small amount of the obtained polyamic acid solution was about 1,405 mPa · s.

Subsequently, 125 g of NMP was added to the resulting polyamic acid solution, and 7.7 g of pyridine and 25 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain white polyimide powder. The imidization ratio of the obtained polyimide powder (polyimide (PI-1)) was measured and found to be 72%.

Preparation Example 201

13.5 g of NMP, 13.5 g of butyl cellosolve (BC) and 13.5 g of? -Butyrolactone were added to and dissolved in 1.70 g of polyimide (PI-1). There was added 0.085 g of 2-benzyl-2-dimethylamino-1- (4-morpholino) -butan-1-one (Irgacure 369 manufactured by BASF) as a polymerization initiator. This solution was filtered with a filter having a pore diameter of 0.45 mu m to prepare a liquid crystal alignment agent 1. [

Preparation examples 202 to 206

Liquid crystal aligning agents 2 to 6 were prepared in the same manner as in Preparation Example 201 except that the kinds of the components to be mixed were changed as shown in Table 3 below. The values shown in Table 3 are parts by mass.

Preparation Example 207

1.86 g (10.0 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (hereinafter referred to as "CBDA"), 2.51 g (7.0 mmol) of a diamine compound represented by the following formula (DA- 1.14 g (3.0 mmol) of the diamine compound represented by the formula (DA-6) was reacted in 22.1 g of NMP for 10 hours, and then 36.8 g of NMP and 27.6 g of BC were added and stirred for 5 hours to obtain a liquid crystal alignment (A).

Further, to 10.0 g of the liquid crystal aligning agent (A) functioning as the first polymerization initiator, 0.06 g (10% by mass based on the solid content) of a polymerizable compound represented by the following formula (RM1) was added and stirred at room temperature for 3 hours To thereby prepare liquid crystal aligning agent 7.

Further, to 10.0 g of the liquid crystal aligning agent (A) functioning as the first polymerization initiator, 0.06 g (10% by mass based on the solid content) of a polymerizable compound represented by the following formula (RM2) was added and stirred at room temperature for 3 hours To prepare Liquid Crystal Alignment Agent 8.

Preparation Example 208

(3.0 mmol) of trimellitic anhydride (hereinafter referred to as "PMDA"), 0.46 g (3.0 mmol) of 3,5-diaminobenzoic acid and 0.73 g (2.0 mmol) of a diamine compound represented by the following formula (DA- ), 0.93 g (2.0 mmol) of a diamine compound represented by the following formula (DA-3) and 1.20 g (3.0 mmol) of a diamine compound represented by the following formula (DA-9) were reacted in 15.9 g of NMP for 30 minutes, g (7.0 mmol) of NMP, and 5.3 g of NMP were further added thereto, followed by further reaction for 10 hours. 35.2 g of NMP and 26.4 g of BC were added and stirred for 5 hours to obtain a liquid crystal aligning agent (C) functioning as a first polymerization initiator.

Further, to 10.0 g of the liquid crystal aligning agent (C) functioning as the first polymerization initiator, 0.06 g (10% by mass relative to solid content) of a polymerizable compound represented by the following formula (RM1) was added and stirred at room temperature for 3 hours To prepare Liquid Crystal Alignment Agent 9.

Preparation Example 209

2.38 g (10.0 mmol) of bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride (hereinafter referred to as "BODA") and the diamine represented by the following formula (DA-2) 2.28 g (6.0 mmol) of a diamine compound represented by the following formula (DA-9) was dissolved in 32.4 g of NMP and reacted at 60 ° C for 5 hours. Then, 1.75 g (9.0 mmol) 10.8 g of NMP was added and reacted at 40 占 폚 for 10 hours to obtain a polyamic acid solution.

NMP was added to 50 g of the polyamic acid solution to dilute it to 6 mass%, then 5.4 g of acetic anhydride and 2.8 g of pyridine as an imidation catalyst were added, and the mixture was reacted at 50 ° C for 3 hours. This reaction solution was poured into 700 mL of methanol, and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (D) which served as a first polymerization initiator. The imidization ratio of the polyimide was 51%, the number average molecular weight was 17,000, and the weight average molecular weight was 38,000.

To 6.0 g of the polyimide powder (D) functioning as the first polymerization initiator thus obtained, 44.0 g of NMP was added and dissolved by stirring at 50 캜 for 5 hours. 6.0 g of a 1 wt% NMP solution of 3-picolylamine, 14.0 g of NMP and 30.0 g of BC were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (D1).

Further, 0.06 g (10% by mass relative to solid content) of a polymerizable compound represented by the following formula (RM1) was added to 10.0 g of the above liquid crystal aligning agent (D1) and dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent 10.

Preparation Example 210

A diamine compound represented by the following formula (DA-3) represented by the following formula (DA-3), a diamine compound represented by the following formula (DA- 2.28 g (6.0 mmol) of the diamine compound represented by the following formula (DA-9) was dissolved in 30.7 g of NMP and reacted at 60 ° C for 5 hours. Then, 1.68 g (9.0 mmol) And the mixture was reacted at 40 DEG C for 10 hours to obtain a polyamic acid solution.

NMP was added to 45 g of this polyamic acid solution to dilute it to 6 mass%, 5.1 g of acetic anhydride and 2.6 g of pyridine were added as an imidization catalyst, and the reaction was carried out at 50 DEG C for 3 hours. This reaction solution was poured into 650 mL of methanol, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 캜 to obtain a polyimide powder (E) serving as a first polymerization initiator. The imidization ratio of the polyimide was 52%, the number average molecular weight was 13,000, and the weight average molecular weight was 27,000.

To 6.0 g of the polyimide powder (E) serving as the first polymerization initiator thus obtained, 44.0 g of NMP was added and dissolved by stirring at 50 DEG C for 5 hours. To this solution, 6.0 g of a 1 wt% NMP solution of 3-picolylamine, 14.0 g of NMP and 30.0 g of BC were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (E1).

Further, to 10.0 g of the above liquid crystal aligning agent (E1), 0.06 g (10% by mass relative to solid content) of a polymerizable compound represented by the following formula (RM1) was added and dissolved by stirring at room temperature for 3 hours, Article 11 was prepared.

Further, to 10.0 g of the above liquid crystal aligning agent (E1), 0.06 g (10% by mass relative to solid content) of a polymerizable compound represented by the following formula (RM2) was added and dissolved by stirring at room temperature for 3 hours, Article 12 was prepared.

Preparation Example 211

(8.0 mmol) of TCA, 1.84 g (8.0 mmol) of 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide and 2.04 g ) And 2.98 g (6.0 mmol) of a diamine compound represented by the following formula (DA-8) were dissolved in 32.0 g of NMP and reacted at 80 ° C for 5 hours. Then, 1.68 g (9.0 mmol) of CBDA and 10.7 g of NMP were added, And reacted at 40 DEG C for 10 hours to obtain a polyamic acid solution.

NMP was added to 45 g of the polyamic acid solution to dilute it to 6 mass%, then 4.9 g of acetic anhydride and 2.5 g of pyridine were added as an imidization catalyst, and the reaction was carried out at 50 ° C for 3 hours. This reaction solution was poured into 650 mL of methanol, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimide powder (F) serving as a first polymerization initiator. The imidization ratio of the polyimide was 50%, the number average molecular weight was 16,000, and the weight average molecular weight was 33,000.

To 6.0 g of the polyimide powder (F) functioning as the first polymerization initiator thus obtained, 44.0 g of NMP was added and dissolved by stirring at 50 캜 for 5 hours. 6.0 g of a 1 wt% NMP solution of 3-picolylamine, 14.0 g of NMP and 30.0 g of BC were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (F1).

Further, 0.06 g (10% by mass relative to solid content) of a polymerizable compound represented by the following formula (RM1) was added to 10.0 g of the above liquid crystal aligning agent (F1) and dissolved by stirring at room temperature for 3 hours, Article 13 was prepared.

The diamine compounds represented by the above formulas (DA-1) and (DA-2) can be synthesized according to Synthesis Example 1 and Synthesis Example 2 of International Publication No. 2015/033921, respectively.

Preparation Example 212

197 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as &quot; ECETS &quot;) as a hydrolyzable silane compound was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, (ECETS: compound represented by the following formula (S-1-1) = 80: 20 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent, triethylamine 10.0 as a catalyst g, and mixed at room temperature.

Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted under reflux at 80 DEG C for 6 hours while stirring. After the completion of the reaction, the organic layer was taken out and washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral. Then, the solvent and water were distilled off under reduced pressure to obtain a hydrolysis-condensation product having an epoxy group As a transparent liquid.

As a result of ¹ H-NMR analysis of the hydrolysis-condensation product, it was confirmed that a peak belonging to the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with the theoretical intensity, and no side reaction of the epoxy group occurred during the reaction .

Subsequently, a 200-mL three-necked flask was charged with the above-obtained hydrolyzed condensate having an epoxy group, and 30.0 g of methyl isobutyl ketone as a solvent and 75.1 g of 4-octyloxybenzoic acid as a carbonic acid 30 mol% based on the total amount of the silane compound and 38 mol% based on the epoxy group of the hydrolyzed condensate) and 36.1 g of 11- (4-cyclohexylphenoxy) undecanoic acid (the hydrolyzable silane compound , And 0.10 g of UCAT 18X (trade name, a curing accelerator of an epoxy compound manufactured by San A Pro Co., Ltd.) as a catalyst were added thereto, and the reaction was carried out at 100 ° C for 48 hours with stirring.

After completion of the reaction, ethyl acetate was added to the reaction mixture, and the resulting organic layer was washed with water three times, dried with magnesium sulfate, and then the solvent was distilled off to obtain a polyorganosiloxane (S-1 ). The weight average molecular weight (Mw) of the polyorganosiloxane (S-1) in terms of polystyrene measured by gel permeation chromatography (GPC) was 8,000.

On the other hand, 220 g (1.0 mol) of TCA as tetracarboxylic dianhydride, 74 g (0.15 mol) of 3- (2,4-diaminophenoxy) cholestane as diamine, 40 g (0.15 mol) of dihydro-1,3,3-trimethyl-1H-inden-5-amine and 110 g (0.7 mol) of 3,5-diaminobenzoic acid were dissolved in 1,800 g of NMP, Time reaction was carried out to obtain a solution containing polyamic acid. The solution viscosity of the obtained polyamic acid solution was measured by collecting a small amount of the polyamic acid solution, which was about 1,300 mPa · s.

Then, 2,200 g of NMP was added to the obtained polyamic acid solution, 120 g of pyridine and 150 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was further replaced with NMP by a solvent to obtain a solution containing about 15 mass% of the polyimide (P-3). The imidization rate of the obtained polyimide (P-3) was about 67%.

A solution in which polyorganosiloxane (S-1) serving as the first polymerization initiator obtained above was dissolved in NMP and a solution containing about 15 mass% of polyimide (P-3) (P-3): polyorganosiloxane (S-1) = 90: 5. Subsequently, NMP and BC were added, and N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane was added to the polyorganosiloxane (S-1) , A solvent composition of NMP: BC = 50: 50 (weight ratio), and a solid content concentration of 6.0% by mass. This solution was filtered using a filter having a pore size of 1 m to prepare liquid crystal aligning agent 14. [

Preparation Example 213

In the synthesis of the polyorganosiloxane (S-1) of Preparation Example 212, the hydrolyzable silane compound used was changed to 246 g of ECETS, and the carbonic acid used was changed to 109.8 g of 4- (4-pentylcyclohexyl) (40 mol% based on the total amount of the hydrolyzable silane compounds used) and 52.9 g of the compound represented by the following formula (C-1-2) (10 mol% based on the total amount of the hydrolyzable silane compounds used as raw materials) The operation was carried out in the same manner as in the synthesis of the organosiloxane (S-1) to obtain 326.9 g of a polyorganosiloxane (S-3) functioning as a first polymerization initiator. The weight average molecular weight (Mw) of the polyorganosiloxane (S-3) in terms of polystyrene measured by gel permeation chromatography (GPC) was 8, 100.

On the other hand, 220 g (1.0 mol) of TCA as tetracarboxylic acid dianhydride, 150 g (0.3 mol) of 3- (2,4-diaminophenoxy) cholestane as diamine and 93 g (0.5 mol) of 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine were dissolved in 2,200 g of NMP, The reaction was carried out at 60 占 폚 for 6 hours to obtain a solution containing polyamic acid. The solution viscosity measured by taking a small amount of the obtained polyamic acid solution was about 1,450 mPa s.

Then, 2,800 g of NMP was added to the obtained polyamic acid solution, 79 g of pyridine and 100 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a further NMP (pyridine and anhydrous acetic acid used in the dehydration ring closure reaction were removed from the system by this operation) to obtain polyimide (P-1) in an amount of about 15 mass% Was obtained. The imidization rate of the obtained polyimide (P-1) was about 51%.

A solution in which polyorganosiloxane (S-3) serving as the first polymerization initiator obtained above was dissolved in NMP and a solution containing about 15 mass% of polyimide (P-1) (P-1): polyorganosiloxane (S-3) = 95: 5. Next, NMP and BC were added to this mixed solution to obtain a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 6.0% by mass. This solution was filtered using a filter having a pore size of 1 탆 to prepare liquid crystal aligning agent 15.

Preparation Example 214

A liquid crystal aligning agent 16 was prepared in the same manner as in Preparation Example 201 except that 2-benzyl-2-dimethylamino-1- (4-morpholino) did.

In the above Tables 1 to 3, the respective components are as follows.

BrDPP: pigment represented by the following formula (BrDPP)

R254: C.I. Pigment Red 254

R177: C.I. Pigment Red 177

Y138: C.I. Pigment Yellow 138

Y139: C.I. Pigment Yellow 139

Y185: C.I. Pigment Yellow 185

G7: C.I. Pigment Green 7

G58: C.I. Pigment Green 58

G59: C.I. Pigment Green 59

B15: 6: C.I. Pigment Blue 15: 6

B16: C.I. Pigment Blue 16

V23: C.I. Pigment Violet 23

AR52: C.I. Acid Red 52 (xanthine dye)

Cya-1: Compound represented by the following formula (Cya-1) (cyanine dye)

Cya-2: The compound (cyanine dye) represented by the following formula (Cya-2)

Pyr-1: a compound (pyrazolone dye) represented by the formula (Pzo) described in JP-A-2015-044982;

BG1: C.I. Basic Green 1 (triarylmethane dye)

BY28: C.I. Basic Yellow 28 (methine dye)

Cou-1: A compound represented by the following formula (Cou-1) (coumarin dye)

Pht-1: A compound represented by the following formula (Pht-1) (phthalocyanine dye, compound No. A-1 described in JP-A No. 2014-177502)

Met-1: a compound represented by the following formula (Met-1) (methine dye)

Dip-1: A compound represented by the following formula (Dip-1) (dipyrromethene dye)

Salt forming compound in a synthesis according to the method described in paragraph [0145] of Japanese Patent No. 5693016 specification, CI Acid Blue 112 and a dialkyl dimethyl ammonium chloride (alkyl is C ₁₄ ~C ₁₈₎ (anthraquinone dye): Ant-1

Xan-1: salt forming compound in a synthesis according to the method described in paragraph [0136] of Japanese Patent Application No. 4.49276 million specification, CI Acid Red 52 and dialkyl dimethyl ammonium chloride (alkyl is C ₁₄ ~C ₁₈₎ (xanthene dye)

BB7: C.I. Basic Blue 7 (triarylmethane dye)

BK1: Irgaphor Black S0100 CF (manufactured by BASF, the compound represented by the above formula (B-1))

BK7: C.I. Pigment Black 7 (carbon black)

BK32: C.I. Pigment Black 32 (perylene black)

Resin-1: The following repeating unit (repeating unit of unsaturated carboxylic acid and repeating unit of unsaturated compound having epoxy group) synthesized according to the method described in "Synthesis of Resin (B-1)" of International Publication No. 2014/192973 ). &Lt; / RTI &gt;

Resin-2: methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / methyl methacrylate / styrene / glycidyl methacrylate = 16/16/38/10/20 (Mass ratio) of an alkali-soluble resin. Mw = 8,000, Mw / Mn = 2.3.

Resin-3: An alkali-soluble resin having a methacryloyloxy group in its side chain, obtained by reacting methacrylic acid with 100 mol% of the epoxy group of Resin-2.

Resin-4: An epoxy acrylate resin synthesized according to the method described in Synthesis Example 3 of JP-A-2008-287246. (The reaction product of the reaction product of an epoxy compound and acrylic acid represented by the above-mentioned general formula (6), biphenyltetracarboxylic acid dianhydride and tetrahydrophthalic anhydride)

DPHA: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

DPEA-12: KAYARAD DPEA-12 (ethylene oxide-modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

TO-1382: Aronix TO-1382 (manufactured by TOAGOSE KOGYO Co., Ltd., a mixture of dipentaerythritol pentaacrylate and monoesters of succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

M1: glycerol methacrylate

M2: a compound represented by the following formula (M2)

M3: pentaerythritol triacrylate

OXE02: Ethanol-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

NCI-930: Adeka Ariz NCI-930 (manufactured by ADEKA Corporation)

NCI-831: Adeka Ariz NCI-831 (manufactured by ADEKA Corporation)

Irg 369: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369,

Irg 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irgacure 907,

OXE01: 1,2- octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime) (trade name Irgacure OXE01,

Ini-1: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-

Irg 379EG: 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name Irgacure 379EG,

Ini-2: 2-methyl-1,2-diphenyl-1-propanone

Dis-1: BYK-LPN21116 (a (meth) acrylic dispersant manufactured by BYK, solid content concentration: 40% by mass)

Dis-2: BYK-LPN6919 (a (meth) acrylic dispersant, a solid content concentration of 60% by mass, manufactured by BYK)

F-554: Megafack F-554 (a fluorochemical surfactant manufactured by DIC Corporation)

FTX-218: Fotogen FTX-218 (manufactured by NEOS Co., Ltd., fluorinated surfactant)

SH8400: Toray Silicone SH8400 (manufactured by Toray Dow Corning Toray Silicone Surfactant)

F781-F: Megafac F781-F (fluorochemical surfactant manufactured by DIC Corporation)

RS-56: Megapack RS-56 (a fluorochemical surfactant manufactured by DIC Corporation)

CW-1: CW-1 (a fluorochemical surfactant manufactured by Zeneca)

Irg1010: Irgacure 1010 (manufactured by BASF, hindered phenol-based antioxidant)

add-1: a chromium complex compound having a ligand having an azo bond represented by the following formula (add-1)

add-2: a tetraazaporphyrin compound represented by the following formula (add-2)

K1: a compound represented by the following formula (K1)

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

CHN: cyclohexanone

DAA: diacetone alcohol

MBA: 3-methoxybutylacetate

EL: Ethyl lactate

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

GBL:? -Butyrolactone

EEP: ethyl 3-ethoxypropionate

Example 1

<Preparation of Substrate for Display Element Having a Chromatic Pattern, Black Spacer and Orientation Layer>

A color filter layer was formed on a substrate on which a switching active element, an electrode, and the like were formed by using each chromatic color composition. A switching active element, a source electrode, a drain electrode, a gate electrode, a source wiring, a gate wiring, and the like are formed on this substrate. These active elements and the like are formed by repeating etching on a substrate by a normal semiconductor film forming film, a known insulating film forming film, and a photolithography method. The color filter layer has an insulating film on the chromatic pattern.

First, a red colored composition (r-1) was applied on a substrate having a switching active element or the like formed thereon by a slit die coater and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film. Thereafter, an exposure amount of 1,000 J / m &lt; 2 &gt; in an i-line conversion was measured using a Canon PLA501F (Canon Inc.) through a predetermined pattern mask using a ghi line (intensity ratio of 436 nm, 405 nm, , Rinsed with ultrapure water for 60 seconds, and further heat-treated in an oven at 220 占 폚 for 60 minutes to obtain a red stripe-like colored pattern having a thickness of 2.0 占 퐉 (Pattern width 100 mu m).

Subsequently, the same procedure was followed to form a green colored pattern on the substrate using the green colored composition (g-1). Further, a chromatic color pattern of blue was formed using a blue chromatic composition (b-1), and chromatic patterns (pattern width 100 m) of three colors of red, green and blue on the substrate were formed.

Next, a known composition for forming an insulating film was applied on the resulting three-color chromatic pattern by a slit die coater. Subsequently, the coating film was prebaked on a hot plate at 90 DEG C for 5 minutes to form a coating film. Subsequently, the obtained coating film was irradiated with a high-pressure mercury lamp at an exposure dose of 700 J / m 2, and the coating film after irradiation with radiation was developed to remove unnecessary portions to form a coating film having a predetermined shape. Further, the film was heat-treated in an oven at 180 캜 for 60 minutes to form an insulating film having a film thickness of 2.0 탆 from the upper surface of the chromatic color patterns of three colors.

Subsequently, a transparent conductive layer made of ITO is formed on the insulating film on the substrate having the insulating film formed on the chromatic pattern by sputtering, and the transparent conductive layer is etched by photolithography to form a transparent electrode .

Next, the black composition (bk-1) was coated on the transparent electrode with a slit die coater. Subsequently, the coating film was prebaked on a hot plate at 100 DEG C for 2 minutes to form a coating film having a film thickness of 6.0 mu m. Subsequently, the obtained coating film was irradiated with a high-pressure mercury lamp at an exposure dose of 700 J / m 2. Subsequently, a developer composed of 0.04 mass% aqueous potassium hydroxide solution at 23 占 폚 was ejected onto the substrate at a developing pressure of 1 kgf / cm2 (nozzle diameter: 1 mm) to form a black spacer pattern on the substrate by performing showering. Subsequently, post baking was performed in an oven at a curing temperature of 180 캜 and a curing time of 30 minutes. Thus, a black spacer was formed on the ITO electrode. The black spacer is formed in a region above the transparent electrode corresponding to the formation region of the switching active element.

Next, on the transparent electrode of the substrate on which the chromatic pattern and the black spacer were formed, the liquid crystal aligning agent 1 was applied by a spinner. Subsequently, pre-baking was performed on a hot plate at 80 DEG C for 1 minute, and then heated in an oven where the inside was replaced with nitrogen at 180 DEG C for 1 hour to form a coating film having a thickness of 80 nm. Subsequently, 200J / m &lt; 2 &gt; of polarized ultraviolet rays including a bright line of 313 nm was irradiated onto the surface of the coating film using a Hg-Xe lamp and a Glane Taylor prism from a direction inclined by 40 DEG with respect to the direction perpendicular to the substrate surface. Thus, a display element substrate having a chromatic pattern, a black spacer, and an alignment film was produced.

<Fabrication of Opposing Substrate and Preparation and Evaluation of Liquid Crystal Display Element>

As a counter substrate, a substrate provided with a transparent common electrode on a transparent substrate was prepared, and an alignment film was formed on the common electrode using the same liquid crystal aligning agent (liquid crystal aligning agent 1) as described above. .

The TN liquid crystal layer was sandwiched between the display substrate and the counter substrate thus obtained to produce a liquid crystal display element having a color filter on array structure. The liquid crystal display element of the color filter-on-array structure of this embodiment exhibited excellent color characteristics and high reliability.

Examples 2 to 36 and Comparative Examples 1 to 4

In the same manner as in Example 1 except that the red chromatic composition, the green chromatic composition, the blue chromatic composition, the black composition and the liquid crystal aligning agent described in Tables 4 to 6 were used in Example 1, A substrate for a display element having a black spacer and an alignment film, and an opposing substrate were prepared. Then, a liquid crystal display element was prepared in the same manner as in Example 1 and evaluated. As a result, all of the liquid crystal display devices of Examples 2 to 36 exhibited excellent color characteristics in comparison with the liquid crystal display devices of Comparative Examples 1 to 4, and showed high reliability.

(Industrial availability)

The display element substrate of the present invention has excellent color characteristics and high reliability. Therefore, the substrate for a display element of the present invention can be suitably used for a large liquid crystal TV which requires excellent display quality and reliability.

1, 31: substrate for display element
4, 24, 104 and 111: substrate
5, 105: source electrode
6, 106: drain electrode
7, 107: gate electrode
8, 108: Switching active element
9, 109: transparent electrode
10: Black spacer
12, 32, 112: chromatic pattern
13, 34: Color filter layer
15, 35: Color filter
17: Contact hole
18: source wiring
19: gate wiring
21, 51, 100: liquid crystal display element
22: opposing substrate
23, 103: liquid crystal layer
25, 114: common electrode
26, 115: alignment film
27, 117: backlight light
28, 116: polarizer
33: Insulating film
101: array substrate
102: Color filter substrate
113: Black Matrix

Claims (12)

1. A substrate for a display element having a switching active element, a chromatic pattern, a black spacer, and an orientation film,
Wherein the black spacer comprises a black colorant,
Wherein the alignment film is formed of a liquid crystal aligning agent containing a first polymerization initiator. The method according to claim 1,
Wherein the first polymerization initiator is at least one selected from the group consisting of a photo-radical generator, a photo-acid generator, a photo-base generator, a thermal acid generator, and a thermal radical generator. The method according to claim 1,
Wherein the alignment film is formed of any one of a polymer having a photo aligning group and a polymer having no photo aligning group and the liquid crystal aligning agent containing the first polymerization initiator. The method according to claim 1,
Wherein the black spacer has an OD (Optical Density) value of 0.3 to 4 per 1 mu m thickness. The method according to claim 1,
Wherein the black colorant comprises at least one member selected from the group consisting of a compound represented by the following formula (B-1), perylene black and carbon black:

(In the formula (B-1), X represents a double bond, and each of the geometric isomers is independently E or Z form, and each R ^a independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, R ^b represents a hydrogen atom, a methyl group, or a phenyl group, and R ^c represents, independently of each other, a hydrogen atom, a methyl group, or a chlorine atom), a fluorine atom, a carboxyl group or a sulfone group. The method according to claim 1,
Wherein the black spacer is formed of a black composition containing a colorant containing a black colorant, a first alkali-soluble resin, and a second polymerization initiator. The method according to claim 6,
Wherein the second polymerization initiator comprises an O-acyloxime compound. The method according to claim 1,
Wherein the chromatic pattern comprises a dye. 9. The method of claim 8,
Wherein the dye is selected from the group consisting of azo dyes, triarylmethane dyes, anthraquinone dyes, xanthene dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, methine dyes, dipyrromethene dyes, cyanine dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes And a quinone imine dye. The method according to claim 1,
Wherein the chromatic pattern is formed of a chromatic composition containing a colorant, a second alkali-soluble resin, a polymerizable compound, and a third polymerization initiator. A manufacturing method of a display element substrate having a chromatic pattern, a black spacer and an alignment film,
A method of manufacturing a substrate for a display element, comprising at least the following steps [1] to [5]:
[1] A process for forming a coating film of a chromatic color composition on a substrate,
[2] a step of curing the coating film of the chromatic color composition to form a colored pattern,
[3] A process for forming a coating film of a black composition on a substrate having a chromatic pattern,
[4] a step of curing the coating film of the black composition to form a black spacer,
[5] A process for forming an alignment film on a substrate on which the black spacer is formed. A display element comprising the display element substrate according to any one of claims 1 to 10.

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