JP2006098673A - Substrate having protrusion for alignment control and liquid crystal display device using the substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress an after image generating when putting a liquid crystal display device, manufactured by using a substrate formed with protrusions for alignment control by using a negative type photosensitive resin composition, in the state of applying a voltage over a long time. <P>SOLUTION: The substrate having at least the protrusions 13, 14 for alignment control holds liquid crystal between a counter substrate and the same to constitute a liquid crystal display device, wherein the protrusions 13, 14 for alignment control are made of the negative type photosensitive resin composition containing a resin having at least phenolic hydroxide group. Further, by using a negative type resist containing a resin having one or more photo-crosslinking functional groups selected from among styryl pyridinium group and styryl quinolium group in one part of side chains of the resin having phenolic hydroxide group, a high-sensitivity negative type photosensitive resin composition may be preferably obtained without injuring electric characteristics. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a vertical alignment (VA) type liquid crystal display (LCD), and more particularly to an alignment control protrusion used in an alignment division vertical alignment (MVA) type multi-domain vertical alignment (MVA) type LCD. And a liquid crystal display device using the same.

  MVA-LCD (Multi-domain Vertical Alignment-Liquid Crystal Display, alignment division vertical alignment type liquid crystal display device, see Patent Documents 1 and 2, Non-Patent Document 1) has a plurality of tilt directions of liquid crystal molecules in one pixel. The vertical alignment type liquid crystal display device which is controlled in this way and is capable of uniform halftone display in all directions, is said to be a liquid crystal display device having excellent contrast, viewing angle characteristics and response speed.

  FIGS. 1A and 1B are explanatory views schematically showing the operation of the MVA-LCD in its cross section. As shown in FIGS. 1A and 1B, a general MVA-LCD (10) includes a TFT side substrate (11) provided with alignment control protrusions (13) via liquid crystal molecules (15). And the color filter side substrate (12) provided with the alignment control protrusions (14). However, the alignment control protrusions (13) and the alignment control protrusions (14) are in alternate positions. It is like that.

  FIG. 1A shows a state when no voltage is applied, and when no voltage is applied, the liquid crystal molecules (15) are vertically aligned between the two substrates, but the alignment control protrusion (13) and the alignment control protrusions. The liquid crystal molecules in part (14) are slightly tilted due to the influence of the slopes of the protrusions. FIG. 1B shows a state when a voltage is applied. When a voltage is applied, the liquid crystal molecules on the slopes of the protrusions begin to tilt, and the liquid crystal molecules other than the tilted portions sequentially have the same orientation. That is, the alignment of liquid crystal molecules is controlled by providing protrusions instead of rubbing treatment.

Conventionally, in order to create such a pattern, a positive resist or a negative resist using an acrylic resin is used, and it has been formed by a photolithography technique (Patent Document 1, Patent Document 2, and Non-Patent Document). 1).

However, the former positive resist has a low yield because common defects are likely to occur, while the negative resist using the latter acrylic resin is superior in sensitivity, patterning characteristics, cost, and process, but has an MVA pattern shape. Depending on the type of liquid crystal, there is a problem that burn-in occurs. Burn-in is a phenomenon in which an afterimage is generated when a voltage is applied for a long time in an MVA-LCD, and the display quality is remarkably lowered. One reason for this is thought to be the accumulation of charges on the surface of the alignment control protrusion, and the solution thereof is an important issue.
Japanese Patent No. 2947350 Japanese Patent Laid-Open No. 11-248921 Electronic Journal October 1997 P.I. 33

Negative resists basically contain a monomer as a curing component in addition to the binder resin, but it has been empirically found that this monomer has an adverse effect on electrical characteristics, so orientation control Reduction of the monomer is required for the composition of the resist for protrusions for use.

  The present invention has been made to solve the above-described problems, and is an MVA-LCD substrate provided with an alignment control protrusion using a negative photosensitive resin composition, and a voltage is applied over a long period of time. It is an object of the present invention to provide a substrate having an alignment control protrusion that does not generate an afterimage even in such a state, and a liquid crystal display device using the substrate.

  As a result of studying various materials and processing methods in order to solve the above-mentioned problems, the present inventor has found that a negative resist having a phenolic hydroxyl group, particularly a styrylpyridinium group in a part of a side chain, as a projection forming material for orientation control Alternatively, by using a negative resist containing a resin having one or more photocrosslinkable functional groups selected from styrylquinolium groups, a color filter having a desired alignment control protrusion can be obtained. It has been found that an MVA liquid crystal display device using a color filter exhibits good display characteristics without burn-in and a wide viewing angle, and has reached the present invention.

  That is, according to a first aspect of the present invention, in the substrate having at least the alignment control protrusion that constitutes the liquid crystal display device that sandwiches the liquid crystal with the opposing substrate, the alignment control protrusion is at least phenolic. A substrate having an alignment control protrusion, which is formed of a negative photosensitive resin composition containing a resin having a functional hydroxyl group.

According to a second aspect of the present invention, there is provided a substrate having at least an alignment control protrusion constituting a liquid crystal display device that sandwiches liquid crystal with an opposing substrate, wherein one of the substrates is at least a transparent substrate and a color An alignment control protrusion comprising a filter layer and provided with an alignment control protrusion formed of a negative photosensitive resin composition containing at least a resin having a phenolic hydroxyl group on the color filter layer. It is a substrate which has.

  According to a third aspect of the present invention, there is provided a substrate having at least an alignment control protrusion that constitutes a liquid crystal display device that sandwiches liquid crystal with the opposing substrate. At least one of the substrates is at least a transparent substrate and a transparent conductive layer. And a substrate having an alignment control protrusion, characterized in that an alignment control protrusion formed of a negative photosensitive resin composition containing a resin having at least a phenolic hydroxyl group is provided on the transparent conductive layer. It is.

  The invention according to claim 4 is characterized in that the resin having a phenolic hydroxyl group has a photocrosslinkable group in a part of a side chain, the alignment control protrusion according to any one of claims 1 to 3 It is a substrate which has.

  The invention according to claim 5 has the alignment control protrusion according to claim 4, wherein the photocrosslinkable group is at least one functional group selected from a styrylpyridinium group or a styrylquinolium group. It is a substrate.

  The invention according to claim 6 is the substrate having an alignment control protrusion according to any one of claims 1 to 5, wherein the resin having a phenolic hydroxyl group has a novolac structure.

According to a seventh aspect of the present invention, the substrate for sandwiching the liquid crystal with the opposing substrate has a spacer projection, and the spacer projection is the same material as the alignment control projection on the same substrate. The substrate having an alignment control protrusion according to claim 1, wherein the substrate has an alignment control protrusion.
By using some of these alignment control projections as a substitute for spacers, the color filter manufacturing process is simplified, and a spacer-less MVA liquid crystal display device substrate and a liquid crystal display device using the same are manufactured. It is also possible to do.

An eighth invention according to an eighth aspect is characterized in that the substrate provided with the alignment control protrusion according to any one of the first to seventh aspects is used for at least one of the opposing substrates sandwiching the liquid crystal. The liquid crystal display device.
An excellent liquid crystal display device in which an afterimage does not occur even when a voltage is continuously applied for a long time, by forming a liquid crystal display device using the substrate having the alignment control protrusion according to any one of claims 1 to 7. Can be provided.

By using a negative photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alignment control protrusion forming material, development is possible with an alkaline aqueous solution, so that conventional processes can be used and electrical characteristics are excellent. And a substrate having an alignment control protrusion on which the charge is difficult to accumulate on the surface of the alignment control protrusion.
By using the substrate having the alignment control protrusions, a substrate and a liquid crystal display device having the alignment control protrusions exhibiting good display characteristics without image sticking and a wide viewing angle can be obtained.

On the other hand, the photocrosslinking reaction of the functional group introduced into a part of the side chain of the resin having a phenolic hydroxyl group is sensitively advantageous in a process performed in air since it does not receive an inhibition reaction by oxygen. Furthermore, among the photo-crosslinkable functional groups, when the styrylpyridinium group or styrylquinolium group is reacted with the side chain of the resin, it is highly sensitive even if the introduction rate is low, so the characteristics inherent to the resin are almost unchanged. It is possible to provide a high level of photosensitivity without loss.
From the above, by using a resin having both of these phenolic hydroxyl groups and one or more photocrosslinkable functional groups selected from a styrylpyridinium group or a styrylquinolium group, no monomer is used or the amount of monomers is greatly increased. Therefore, a negative resist having excellent electrical characteristics and sensitivity can be obtained.

By forming a spacer replacement protrusion when forming the alignment control protrusion according to the present invention, the manufacturing process of the color filter is simplified and the spacer-less MVA liquid crystal display device substrate and the liquid crystal display device using the same Can also be manufactured.
Furthermore, in the present invention, independent protrusions are formed on the black matrix of the color filter by the same technique, and the independent protrusions are used as a spacer substitute for maintaining a uniform cell gap when assembling the cells. It is also suitable for obtaining a substrate having a color filter function and a spacer replacement protrusion, which can provide a color liquid crystal display device of the type.

Hereinafter, embodiments of the present invention will be described in detail.
The present invention relates to a substrate having at least alignment control protrusions or a liquid crystal display device using the same, which constitutes a liquid crystal display device in which liquid crystal is sandwiched between opposing substrates, and particularly to an alignment division vertical alignment type LCD. It is a liquid crystal display device used for the above.

  Hereinafter, in the present specification, a substrate in which a color filter layer is provided on a light-transmitting substrate and an alignment control protrusion is formed thereon is mainly described. This is a substrate or a liquid crystal display device according to the present invention. However, this does not mean that the color filter layer must be provided.

As the substrate constituting the substrate having the alignment control projections of the present invention, a plate-like substrate having translucency is preferable, such as glass, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polyacrylate, or the like. A plastic sheet or film may be mentioned.
In addition, since the heating process is performed after forming the alignment control projections, a glass substrate excellent in heat resistance is preferable, and furthermore, a glass having a low coefficient of thermal expansion and excellent dimensional stability in the heating process is selected. Is preferred.

A color filter layer can be formed on a substrate having alignment control projections of the present invention and used as a liquid crystal color filter.
In the MVA liquid crystal display device, the substrate having the alignment control protrusions having the color filter function may include a transparent protective film layer and a transparent conductive layer on a pixel (color filter layer) in a normal color filter as necessary. And having a specific alignment control protrusion.

In general, a color filter is formed by forming a black matrix (K) for improving contrast on a transparent substrate, and then a colored pixel layer of red (R), green (G), and blue (B). When this is used for liquid crystal, a transparent conductive layer and an alignment film layer are sequentially laminated. For example, an LCD is placed through a liquid crystal layer by facing a counter substrate on which an electrode such as a thin film transistor is formed. It constitutes.
In this specification, the black matrix and the red, green, and blue colored pixel layers are collectively referred to as a color filter layer.

  The black matrix constituting the color filter layer can be formed using a known method. For example, a thin film of a metal or metal oxide such as chromium or titanium is formed on a substrate by a method such as sputtering, and then patterned by a technique such as etching. Alternatively, light-shielding fine particles such as carbon black and metal oxides and colorants such as pigments or dyes are mixed in the photosensitive resin composition, and this is formed as a photosensitive resin layer on the substrate to perform photolithography. Formed by law. Alternatively, there may be mentioned, for example, one formed by laminating two or more colored pixel layers composed of R, G, B, etc., which will be described later, but any method may be used in the present invention.

  The colored pixel layer is provided in the opening of the black matrix, and a pixel pattern composed of three primary colors, usually a red pixel pattern (R), a green pixel pattern (G), and a blue pixel pattern (B), is arranged in a desired shape. It is a thing. As the formation method, there are already known methods such as a pigment dispersion method, a dye method, an electrodeposition method, a printing method, a transfer method and a method of forming each pixel by ink jetting. In the present invention, any method is used. Also good.

  As an embodiment of the substrate having alignment control protrusions in the present invention, a configuration in which alignment control protrusions are provided on the color filter layer or the transparent conductive layer, or a color filter layer, a transparent conductive layer, and an alignment control protrusion. The structure is formed in the order of the alignment film layers, or if necessary, consists of a plurality of layers provided with a protective film layer between any of these layers.

The transparent conductive film layer is an essential component for at least one of the substrates used for the liquid crystal display device, which sandwiches the liquid crystal with the opposing substrate. Normally, it is formed directly under an alignment film or alignment protrusion that regulates the alignment direction of the liquid crystal, and the behavior of the liquid crystal sandwiched between the substrates is controlled by transmitting an electric signal. Alternatively, it can be provided by vapor deposition or the like on the upper layer of the alignment protrusion.
The transparent conductive layer is made of a material that is transparent and conductive and can be formed into a thin film. Usually, an ITO (indium and tin composite oxide) film is used, and IZO (indium and zinc composite oxide) and SnO are used. _{2 A} (tin dioxide) film or the like is selected, and each is formed by a technique such as sputtering or vacuum deposition.

  At least one of the substrates constituting the liquid crystal display device of the present invention is provided with an alignment film layer, which is different from the alignment control protrusion. For the alignment film layer, a negative liquid crystal compound is vertically aligned and a transparent and insulating material is used. Usually, a polyimide resin is used, and a polyimide resin solution, a polyamic acid solution, or the like is formed by a known coating method or printing method, and then fired.

  The protective film layer provided as necessary is for flattening the level difference generated when the black matrix and the colored pixel layer are formed, or for the components contained in the black matrix and the colored pixel layer to be mixed into the liquid crystal layer. It is something to prevent and requires transparency. Examples of the material for forming the protective film layer include photocurable, thermosetting, light and thermosetting resin compositions, resin cured products such as epoxy, acrylic and polyimide, and inorganic compounds by sputtering and vapor deposition. Any material can be used as long as the object can be achieved. In consideration of the surface state of the color filter layer, it can be formed in the range of 0.5 to 3 μm.

  A substrate used for an MVA-LCD generally has a specific alignment control protrusion via a transparent protective layer and a transparent conductive layer as necessary on a pixel in a normal color filter. If an ordinary negative photosensitive resin composition is used in order to obtain an alignment control projection with high dimensional accuracy, the spread of the base becomes too large to obtain an orientation control projection having a desired shape. In addition, it is difficult to obtain the alignment control protrusions with high dimensional accuracy, particularly when the substrate is enlarged, and the developer resistance of the hardened portion is very important. In addition, since the obtained color filter having alignment control protrusions is applied with an alignment film, the alignment control protrusions themselves are required to have a high degree of heat resistance and solvent resistance, and the alignment film has a polarity through the alignment film thin film. Since it is exposed to liquid crystal, ionic impurities are hardly eluted and excellent electrical characteristics are required.

  As a material for providing alignment control protrusions having such required characteristics, the present inventors are excellent in negative resists containing a phenolic hydroxyl group and a resin having a photocrosslinkable group in a part of the side chain. I found out. It is empirically known that a phenolic hydroxyl group can be developed with an aqueous alkaline solution, so that a conventional process can be used and it exhibits excellent electrical characteristics. In addition, the photocrosslinking reaction is not susceptible to polymerization inhibition by oxygen, and thus is sensitively advantageous in a process performed in air. In particular, among the photocrosslinkable functional groups, when the styrylpyridinium group or styrylquinolium group is reacted with the side chain of the resin, it is highly sensitive even if the introduction rate is very low. Photosensitivity can be imparted without loss. Furthermore, by using a resin that has both a crosslinkable functional group selected from a phenolic hydroxyl group and a styrylpyridinium group or a styrylquinolium group, a combination of these is used, or the amount of monomer is reduced. Therefore, a negative photosensitive resin composition having excellent electrical characteristics and sensitivity can be obtained.

The method for synthesizing a resin having a phenolic hydroxyl group and having at least one photocrosslinkable group selected from a styrylpyridinium group or a styrylquinolium group in the side chain, contained in the negative photosensitive resin composition used in the present invention, The method is not particularly limited, and can be performed by a known general synthesis method such as a polymer reaction. For example, photosensitive polymer (Gentaro Nagamatsu, Hideo Miki, published by Kodansha) and research report on fiber polymer material research laboratory (Institute of Industrial Science and Technology, fiber polymer material research laboratory) No. 155 p. 29-35), a styrylquinolium salt compound is glycidylated, this terminal glycidyl group and a hydroxyl group of a resin having a phenolic hydroxyl group are subjected to an addition reaction to introduce a photosensitive group into the side chain of the resin. Further, a method of adding a sulfonic acid compound or the like to quaternize and increase the sensitivity can be used.

  The resin having a phenolic hydroxyl group includes, for example, an alkali-soluble phenol resin, and the synthesis method is not particularly limited. For example, phenols and aldehydes are condensed in the presence of an acid catalyst. And a known method such as polymerizing a vinyl group of vinylphenol. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol C or bisphenol A. These phenols are used alone or in combination of two or more. Examples of the aldehydes include aliphatic or aromatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde. Among these, a resin including a novolac structure is preferable from the viewpoint of electrical characteristics and ease of handling, and a cresol novolac resin is particularly preferable. In addition, if necessary, the molecular weight distribution of the resin may be adjusted using a means such as fractionation.

  In order to impart photosensitivity to the negative photosensitive resin composition used in the present invention, the resin having a phenolic hydroxyl group preferably has a photocrosslinkable group. More preferably, it has a photocrosslinkable group selected from a styrylpyridinium group or a styrylquinolium group, and examples of the compound having such a functional group include 2- [2- (3-methoxy-4-hydroxy) phenyl ether. And styrylpyridinium salt compounds such as [tenyl] pyridine or styrylquinolium salt compounds. These can be synthesized from, for example, a heterocyclic compound having an active methyl group and hydroxybenzaldehyde by a known method. These are usually used alone, but can be used in combination of two or more as required.

  The introduction ratio of these photocrosslinkable groups is desirably adjusted to 0.01 to 20 mol% with respect to the phenolic hydroxyl group, and more preferably in the range of 0.1 to 5%. If the introduction rate is less than 0.01 mol%, the sensitivity required during production cannot be obtained. On the other hand, if the introduction rate is 20 mol% or more, the storage stability is poor and the alkali solubility of the resin is reduced. However, the developability of the resist is remarkably lowered, and the electrical characteristics are also deteriorated because the original characteristics of the resin are impaired.

A negative resist solution that provides a protrusion pattern in the color filter of the present invention can be obtained in this way, but can also be used in combination with other photocuring reaction systems to further improve sensitivity and cure density. The photocuring reaction system includes a photoradical polymerization reaction comprising a (meth) acryl monomer and a photoradical polymerization initiator, a photocationic polymerization reaction comprising an alicyclic monomer such as epoxy or oxetane and a photocationic polymerization initiator, an azide compound. Known reaction systems such as other photo-crosslinking reactions consisting of, and the like can be mentioned. A combination of these reaction systems, high sensitivity, imparting wavelength selectivity, heat resistance, and chemical resistance may be improved as necessary.

However, it has been empirically known that the monomer has an adverse effect on the electrical characteristics, and the amount thereof needs to be minimized. The upper limit of the amount varies greatly depending on the type of resin used, the introduction ratio of the photosensitive group, the type of monomer, and the like, but it is desirable to keep it to 50% by weight or less, preferably 40% by weight or less based on the resin.

  In addition to the above-mentioned components, the negative photosensitive resin composition of the present invention is compatible with additives as necessary, such as for improving applicability, adhesion, heat resistance, and chemical resistance, such as a plasticizer. Stabilizers, surfactants, colorants, leveling agents, coupling agents, fillers, and the like can be added as long as the object of the present invention is not impaired.

  In preparing the photosensitive solution, it may be diluted with an appropriate solvent as necessary, but in that case, drying is required after coating on the substrate. Examples of the solvent include dichloromethane, chloroform, acetone, 2-butanone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethylethoxyacetate, 2-butoxyethyl acetate, 2-methoxy Ethyl ether, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane and the like.

  Next, a method for forming the alignment control protrusion of the present invention will be described. On the substrate having translucency or, if necessary, the above-described negative photosensitive resin composition on the substrate on which the color filter layer, the transparent conductive layer, and the protective film layer are laminated by the above-described method, Lamination is performed using a known coating method such as a bar coater, applicator, wire bar, spin coater, roll coater, slit coater, curtain coater, die coater or comma coater.

  Thereafter, a photomask having a predetermined pattern is brought into close contact, light exposure is performed to perform pattern exposure, development is performed, and unexposed portions are dissolved and removed to form alignment control protrusions.

  In the pattern exposure, for example, by exposure with an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a halogen lamp, etc. An MVA image faithful to the mask pattern can be obtained. Further, if necessary, the film can be hardened by heat treatment.

  The alignment control protrusions in the present invention are subjected to a heating step after the photolithography process, thereby promoting the curing of the alignment control protrusions and improving the adhesion to the substrate, and further imparting solvent resistance and chemical resistance. In addition, the shape can be made smooth by heat shrinkage and reflow, and the orientation of liquid crystal molecules can be further improved.

  The shape of the alignment control protrusion is preferably regular, such as a dot shape, a stripe shape, or a zigzag shape, and its cross section is a semicircular shape, a semielliptical shape, or a polygonal shape such as a triangle. It is preferable. The pattern on the pixel is not particularly limited as long as the pixel is divided into two or more parts together with the alignment control protrusion on the counter substrate.

  Furthermore, by utilizing a part of these protrusions as a substitute for the spacer, it is possible to simplify the color filter manufacturing process and manufacture a spacer-less MVA liquid crystal display device excellent in cost.

  Hereinafter, embodiments of the present invention will be described with reference to specific examples, but the present invention is not limited to the examples described below. Further, since the negative photosensitive resin composition used in the present invention is extremely sensitive to light, it is necessary to prevent exposure to unnecessary light such as natural light, and all operations are performed under a yellow or red light. Needless to say.

<< Synthesis of SbQ-modified novolak resin >>
<Synthesis of stilbazole>
In 89 g of acetic anhydride, 53 g of vanillin and 35 g of 2-methylpyridine were reacted under reflux for 8 hours, and acetic acid was distilled off from the product at normal pressure. After cooling, concentrated hydrochloric acid was added, left at room temperature for 30 minutes, heated at 80 to 90 ° C., cooled again, dispersed in water, added with aqueous ammonia, and further stirred at room temperature for 2 hours. The obtained pale yellow crystals were collected by filtration, washed with water, and then dried under reduced pressure at 40 ° C. for 12 hours to obtain 55 g of stilbazole.

<Glycidyl etherification of stilbazole>
55 g of stilbazole and 50 g of epichlorohydrin were dissolved in cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), 10 g of powdered sodium hydroxide was added little by little, and reacted at 30 ° C. for 4 hours. Excess epichlorohydrin was removed under reduced pressure, and water was added to dissolve the produced salt, followed by separation and removal. Further, the solution was dried using magnesium sulfate and filtered to obtain 48 g of glycidylated stilbazole.

<Addition reaction of stilbazole to cresol novolac resin>
120 g of cresol novolak resin (EP4050G, manufactured by Asahi Organic Materials Co., Ltd.) and 2.82 g of the above glycidylated stilbazole were dissolved in 500 g of cyclohexanone, and 0.1 g of SA-102 (DBU-octylate) was added as a catalyst under reflux. The reaction was carried out for 1 hour. Further, 1.88 g of methyl p-toluenesulfonate was added and reacted at 50 ° C. for 12 hours to obtain the intended SbQ-modified novolak resin solution A.

  1 g of a leveling agent was mixed and dissolved in 100 g of the resin solution A, followed by filtration with a 0.2 μm filter to prepare a negative photosensitive resin composition.

  A Cr thin film was formed on a transparent substrate, and a black matrix was formed by a photoetching method. A red photosensitive resin composition is applied thereon, exposed to light, developed, and post-baked to form red pixels, and then the same processing is performed on the green photosensitive resin composition and the blue photosensitive resin composition. A green pixel and a blue pixel were formed.

  Next, an ITO film is formed on the entire surface by sputtering, and further, the negative photosensitive resin composition is applied to a thickness of 1.9 μm with a spin coater. Development processing was performed to form a line pattern having a line width of 10 μm. Subsequently, post-baking was performed at 230 ° C./45 minutes to obtain a substrate for an MVA liquid crystal display device having a color filter layer and alignment control protrusions.

The negative photosensitive resin composition thus obtained was cured at 120 mJ / cm ² and the patterning characteristics were good. Further, when an MVA type liquid crystal display device was produced using a substrate having alignment control projections made of this negative photosensitive resin composition, this MVA type liquid crystal display device had a high viewing angle and voltage for a long time. Even in the state in which no is applied, image sticking did not occur and good display performance was exhibited.

<Synthesis of SbQ-modified polyvinylphenol resin>
SbQ-modified polyvinyl phenol resin solution B was obtained in the same manner as in Example 1 except that 134 g of polyvinyl phenol resin (S-4P, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 120 g of cresol novolac resin.

  1 g of a leveling agent was mixed and dissolved in 100 g of the resin solution B, followed by filtration with a 0.2 μm filter to prepare a negative photosensitive resin composition. The negative photosensitive resin composition thus prepared was used in the same manner as in Example 1 to obtain an MVA liquid crystal display substrate having a color filter layer and alignment control protrusions.

The negative photosensitive resin composition thus obtained was sufficiently cured at 150 mJ / cm ² and had good patterning characteristics. Further, when an MVA type liquid crystal display device was produced using a substrate having alignment control projections made of this negative photosensitive resin composition, this MVA type liquid crystal display device had a high viewing angle and burn-in occurred. The display performance was good.

  10 g of dipentaerythritol hexaacrylate (Aronix M-402, manufactured by Toagosei Co., Ltd.) as a radical photopolymerizable monomer and 100 g of Irgacure 369 (manufactured by Ciba Specialty Chemicals) as an initiator are added to 100 g of the resin solution A. After 1 g of the leveling agent was mixed and dissolved, the mixture was filtered with a 0.2 μm filter to prepare a negative photosensitive resin composition. The negative photosensitive resin composition thus prepared was used in the same manner as in Example 1 to obtain an MVA liquid crystal display substrate having a color filter layer and alignment control protrusions.

The negative photosensitive resin composition thus obtained was cured at 80 mJ / cm ² and had good patterning characteristics. Further, when an MVA type liquid crystal display device was produced using a substrate having alignment control projections made of this negative photosensitive resin composition, this MVA type liquid crystal display device had a high viewing angle and burn-in occurred. The display performance was good.

[Comparative Example 1]
100 g of a resin (PVA-SBQ, SPP-LS-400, manufactured by Toyo Gosei Co., Ltd.) obtained by addition polymerization of a styrylpyridinium salt compound to a part of the side chain of polyvinyl alcohol is dissolved in 200 g of water and 1 g of a leveling agent is mixed. After dissolution, the mixture was filtered through a 0.2 μm filter to prepare a negative photosensitive resin composition. PVA-SbQ used here is a commercial product, but may be synthesized by a known method. A substrate for an MVA type liquid crystal display device having the color filter layer and the alignment control protrusions is operated in the same manner as in Example 1 except that the negative photosensitive resin composition thus prepared is used and water is used as a developer. Got.
Research Report on Fiber Polymer Materials Research Institute (Institute of Technology) 29-35

The alignment control protrusions thus obtained were cured at 80 mJ / cm ² and had good patterning characteristics. However, when an MVA type liquid crystal display device was produced using a substrate having alignment control projections made of this negative photosensitive resin composition, the MVA type liquid crystal display device was burned when a voltage was applied for a long time. I have.

[Comparative Example 2]
Except that 20 g of dipentaerythritol hexaacrylate (Aronix M-402, manufactured by Toagosei Co., Ltd.) and 3 g of Irgacure 369 (manufactured by Ciba Specialty Chemicals) were added as components of the negative photosensitive resin composition. And operated.

The alignment control protrusions thus obtained were cured at 50 mJ / cm ² and had very high sensitivity. However, when an MVA type liquid crystal display device was produced using a substrate having alignment control projections made of this negative photosensitive resin composition, the MVA type liquid crystal display device was burned when a voltage was applied for a long time. I have.

It is explanatory drawing which shows the board | substrate for liquid crystal display devices which formed the alignment protrusion by the method which concerns on this invention.

Explanation of symbols

10 ... MVA-LCD
DESCRIPTION OF SYMBOLS 11 ... TFT side substrate 12 ... Color filter side substrate 13 ... Orientation control protrusion 14 ... Orientation control protrusion 15 ... Liquid crystal molecule

Claims (8)

  A negative photosensitive resin comprising a liquid crystal display device that sandwiches liquid crystal with an opposing substrate and having at least alignment control protrusions, wherein the alignment control protrusions include a resin having at least a phenolic hydroxyl group. A substrate having alignment control protrusions, characterized by being formed of a composition.   In a substrate having at least an alignment control protrusion, which constitutes a liquid crystal display device that sandwiches liquid crystal with an opposing substrate, at least one of the substrates is composed of at least a transparent substrate and a color filter layer, on the color filter layer A substrate having an alignment control protrusion, which is provided with an alignment control protrusion formed of a negative photosensitive resin composition containing a resin having at least a phenolic hydroxyl group.   In a substrate having at least an alignment control protrusion, which constitutes a liquid crystal display device that sandwiches liquid crystal with the opposing substrate, at least one of the substrates is composed of at least a transparent substrate and a transparent conductive layer, on the transparent conductive layer A substrate having an alignment control protrusion, characterized in that an alignment control protrusion formed of a negative photosensitive resin composition containing a resin having at least a phenolic hydroxyl group is provided.   4. The substrate having an alignment control protrusion according to claim 1, wherein the resin having a phenolic hydroxyl group has a photocrosslinkable group in a part of a side chain.   5. The substrate having an alignment control protrusion according to claim 4, wherein the photocrosslinkable group is one or more functional groups selected from a styrylpyridinium group and a styrylquinolium group.   6. The substrate having alignment control protrusions according to claim 1, wherein the resin having a phenolic hydroxyl group has a novolac structure.   The substrate for sandwiching the liquid crystal with the opposing substrate has a spacer projection, and the spacer projection is formed of the same material as the alignment control projection on the same substrate. Item 7. A substrate having an alignment control protrusion according to any one of Items 1 to 6.   8. A liquid crystal display device, wherein the substrate provided with the alignment control protrusion according to claim 1 is used as at least one of opposing substrates sandwiching liquid crystal.

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