JPH0876129A - Liquid crystal display element and its production - Google Patents

Abstract

PURPOSE: To obtain a liquid crystal display element having uniform orientational property and no display irregularity. CONSTITUTION: This liquid crystal display element consists of a substrate 1 having stripe-like electrodes 4a and oriented film 11a successively formed on the inner surface, a substrate 2 having stripe-like electrodes 4b stretching in the perpendicular direction to the electrodes 4a and oriented films 11a successively formed on the inner surface, a liquid crystal 13 held between these substrates 1, 2, and a spacer 3 to maintain the distance between the substrates 1, 2. The spacer 3 consists of such a product obtd. by heating a positive photosensitive polymer (a compd. of polymer having carboxyl groups and including a base- producing agent) which can be developed with water and depositing and fixing the product to the oriented film 11b on the substrate 2. Further, the spacer is located in the region of a black matrix layer 5 which surrounds the pixel part in the intersection area of electrodes 4a, 4b. The spacer 3 is formed by applying a photosensitive polymer on the orientation controlling layer, exposing the polymer to light through a light-shielding mask, developing with water and baking.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device,
In particular, the present invention relates to a liquid crystal display device characterized by using a water-developable positive photosensitive polymer for a spacer member for keeping a constant space between substrates of the liquid crystal display device, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In a conventional super twist type liquid crystal display element, the major axis of liquid crystal molecules is twisted by 180 degrees or more between two substrates, and an active matrix type liquid crystal display element is an active matrix type electrode substrate. The above is what drives the liquid crystal. In order to keep the distance between these substrates constant, spacer particles (polymer true spheres, inorganic spherical silica) are generally arranged between 100 to 200 particles / mm ² between the substrates, and the vibration and shock of the liquid crystal screen. It is necessary to firmly fix the spacer particles to the alignment control film in order to reduce the occurrence of defects and unclear screens due to the above. JP-A-60-262
No. 129, a liquid crystal display device is manufactured by forming a solvent containing spacer particles in an alignment control film member on a substrate and fixing the spacer particles with an alignment control layer to manufacture a liquid crystal display device. No. 2129 discloses that liquid crystal display elements are manufactured by spraying spacer particles on a substrate in a state where the solvent of the orientation control layer is not solidified and fixing the spacer particles by solidifying the solvent. In Japanese Patent Publication No. 44631-200, after applying a polyimide and performing an alignment treatment by rubbing, 200 ° C.
A spacer particle coated with a low-temperature softening polymer which is softened at the following temperature is evenly dispersed to produce a liquid crystal display device. JP-A-61-196230 discloses a polyimide in which the spacer is not photosensitive. Is patterned with a photoresist agent, or is itself patterned from a photosensitive polyimide precursor and has a cell thickness of 2
Grow smectic phase monodomain below μm,
There are proposals for manufacturing a ferroelectric liquid crystal element.

[0003]

The conventional spacer particles (polymer true spherical particles, inorganic spherical silica) in the liquid crystal display device using the spraying method regardless of the pixel portion and the non-pixel portion have the following various problems. There's a problem. First, in the method of applying the solvent of the alignment film member mixed with the spacer particles onto the substrate (flexo printing, gravure printing, spinner), the orientation control layer cannot be applied uniformly due to the presence of the spacer particles, Then, the spacer particles are likely to be agglomerated in the solvent of the alignment film member, the cell thickness of the liquid crystal element cannot be ensured uniformly, and the spacer ratio is reduced due to the presence of the spacer particles in the pixel portion. There is. Next, the fixing force of the spacer particles fixed to the orientation control layer can be expected to some extent,
It is not sufficient depending on the season, temperature, or vibration intensity, and is weak and extremely unstable. In particular, display unevenness caused by movement of spacer particles when the liquid crystal is sealed in the display element is a problem. Further, after fixing the spacer particles by the orientation control layer, if rubbing treatment is carried out, the orientation control layer is not uniform due to the presence of the spacer particles and the orientation is apt to become non-uniform. There is also a problem that defects are generated in the orientation of the portion because of the tendency to fall off. When an adhesive layer is formed on the surface of the spacer particles and the spacer particles are fixed on the substrate, agglomeration easily occurs between the spacer particles and the uniformity of cell thickness control of the liquid crystal layer is impaired. ing. On the other hand, if the spacer is a patterning of a non-photosensitive polyimide using a photoresist agent or is itself patterned from a photosensitive polyimide precursor, a process such as coating or peeling of the photoresist is included. In addition, there is a problem in that the dimensional accuracy is lowered and the orientation becomes non-uniform due to the use of an organic solvent, the complicated process, and the transfer through a resist. Therefore, in order to simplify the microfabrication process and improve its precision, it is necessary to perform microfabrication with direct light. At that time, in the negative-type photosensitive material, swelling of the exposed part due to the organic solvent causes high-resolution microfabrication. However, there is a problem in that non-uniformity of alignment occurs unless it is a positive photosensitive polymer for water development.

In order to solve the above-mentioned problems, the present invention forms a positive type photosensitive polymer newly containing a base generator in a polymer of a carboxyl group on an orientation control layer and exposes it through a light-shielding mask. , An attempt was made to form a spacer pattern by performing a water development process. As a result, good spacers could be provided on the orientation control layer on the substrate surface.

It is an object of the present invention to provide a liquid crystal display device in which spacers are evenly distributed, the orientation of the orientation control layer is uniform, and display unevenness is prevented, and a manufacturing method thereof.

[0006]

In order to achieve the above object, the present invention uses the following technical means. The means is a method of performing a water development process using a positive photosensitive polymer characterized in that a polymer containing a carboxyl group contains a photobase generator that generates a base upon irradiation with electromagnetic waves. In particular, the contrast ratio can be greatly improved by forming the spacer in the region of the black matrix layer in the non-pixel portion.

For example, the base generator is represented by the general formula (Ι)

[0008]

Embedded image

The effect of the present invention is more enhanced when the compound represented by That is, the solubility of the polyamic acid molecule by including the compound of the base generator,
This is achieved by utilizing the fact that it greatly changes due to the presence of a base. Therefore, any compound having a carboxylic acid group in its chemical structure can be applied. The number average molecular weight of the carboxylic acid is 1 when the mechanical properties of the Relief pattern are taken into consideration.
It is preferably 0000 or more, and the upper limit of the molecular weight is not particularly limited, but is 100 when the solubility is taken into consideration.
000 or less is desirable. After forming a relief image of polyamic acid, it is possible to obtain a relief image having good heat resistance and chemical resistance by heating at low temperature or chemically imidizing it to convert it to polyimide, polyimidesiloxane, polyamideimide or the like. Therefore, it exhibits excellent performance as a spacer member of a liquid crystal display device. The polyamic acid used in the present invention can be obtained by reacting a diamine or dihydrazide with a tetracarboxylic acid or its derivative. Examples of tetracarboxylic acid derivatives include acid anhydrides and acid chlorides. The use of an acid anhydride is preferable in terms of reactivity and by-products. Examples of the diamine and acid anhydride derivative used in the present invention include the compounds described in JP-A-61-181829.

Specific compounds include cyclohexylparatoluenesulfonylamine, [[(3,5-dimethylbenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N. -[[(2,6-Dinitrophenyl) -1-methylmethoxy] carbonyl] cyclohexylamine, N-[[(2,6-dinitrophenyl) -1- (2 ', 6'-dinitrophenyl) methoxy]
Carbonyl] cyclohexylamine, N-[[(2-nitrophenyl) -1- (2-nitrophenyl) methoxy]
Carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, N-[[(2-nitrophenyl) -1-methylmethoxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy ] Carbonyl] piperidine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine and the like can be mentioned. Also, α-ketocarboxylic acid ammonium salt, phenylglyoxylic acid ammonium salt, 4-methylphenylsulfonamide, N-
Cyclohexyl-4-methylphenyl sulfonamide and the like can also be used. All of these compounds decompose by irradiation with electromagnetic waves to generate a base. In particular, the base generator represented by the formula (I) is an excellent spacer member with high generation efficiency. The group represented by R ₁ in the structural formula is preferably an organic group having 10 or less carbon atoms from the viewpoint of film slippage during the formation of the relief pattern. In addition, the photobase generator used in the present invention can be used regardless of the above structure as long as it can generate a water-soluble aliphatic amine by irradiation of electromagnetic waves. In the present invention, the electromagnetic wave has a wavelength of 10 μm
It is desirable to use a light beam of 1 nm, preferably 200 to 900 nm.

The present invention has been achieved by mixing a polyamic acid synthesized by the above-mentioned conventional method with a base generator, and is used in combination with a sensitizer, an adhesion improver composed of various amine compounds, a surfactant and the like. It goes without saying that they can be used in combination.

The base generated by light irradiation reacts with the carboxylate in the polymer and changes the solubility of the polymer. That is, the portion where the base and the carboxylic acid react to form a salt has improved solubility in water and reduced solubility in an organic solvent. As a result, a positive image is obtained when highly polar water is used as the developing solution. Since the bond between the carboxylic acid group and the generated base is weak, it can be easily eliminated in the imidization process at a low temperature to give an excellent film quality relief pattern. Since the above-mentioned release pattern is based on salt formation, the amounts of carboxylic acid and base generator in the resin composition are important. As a result of studying the blending amount of these, it was found that a good relief pattern was obtained when the carboxylic acid was 20% by weight or more based on all the resin components. The amount of base generator is 0.2 to 2.
It was found that a good relief pattern was obtained at 0 molar equivalent.

[0013]

With the constitution of the present invention, the base generated by light irradiation reacts with the carboxylic acid group in the polymer, changes the solubility of the polymer in water, and enables development between the unexposed area To Since the bond between the carboxylic acid salt and the generated base or the carboxylic acid group and the base generator is weak, it is easily desorbed to give an excellent film quality relief pattern. In the present invention, a positive photosensitive polymer containing a base generator is newly formed on a polymer containing a carboxyl group on the alignment control layer, and light exposure and water development treatment are performed through a light-shielding mask to perform a space-saving process. -The support member formed a pattern having a rectangular or non-spherical shape.
As a result, the spacers are uniformly distributed on the alignment control layer on the substrate surface, and the spacers are not aggregated, so that the nonuniformity of the alignment is not observed and the spacers are firmly fixed. Therefore, a liquid crystal display element in which display unevenness does not occur without moving the spacer when the liquid crystal is sealed is provided.

[0014]

EXAMPLES The liquid crystal display device of the present invention will be described in detail below with reference to examples.

[Embodiment 1] FIG. 1 is a plan view showing the structure of a liquid crystal display element according to an embodiment of the present invention, and FIG.
-II is a sectional view. This liquid crystal display element is configured to hold a liquid crystal 13 in an internal space formed by a spacer 3 between a first substrate 1 and a second substrate 2 facing each other. More specifically, on the inner surface of the first substrate 1, the black matrix layer 5 and the color filter layer 8 arranged in the surface of the layer 5 are further planarized by sequentially covering the black matrix layer 5 and the color filter layer 8. Layer 10,
An electrode 4a and an alignment film 11a are provided, and a polarizing plate 9a is provided on the outer surface of the substrate 1. On the other hand, a striped electrode 4a and a flat alignment film 11b covering the electrode 4a are provided on the inner surface of the second substrate 2, and a phase plate 12 and a polarizing plate 9b are sequentially provided on the outer surface of the substrate 2. It is provided. The spacer 3 is arranged between the alignment films 11a and 11b, and a seal 6 for enclosing the liquid crystal 13 is provided around the substrates 1 and 2.

In this liquid crystal display device, the black matrix layer 5 (hatched portion) prevents the contrast from being lowered due to the transmitted light around the pixel electrode formed of the color filter layer 8, the electrodes 4a and 4b drive the liquid crystal, and the alignment films 11a and 11a. 11b controls the orientation of liquid crystal molecules, the polarizing plates 9a and 9b control the transmission or blocking of light, the flattening layer 10 covers the surface of the color filter layer 8 to provide flatness, and the phase plate 12 is They are provided for achromatic display.

For the first substrate 1 and the second substrate 2, a transparent glass plate having a size of 270 × 200 mm and a thickness of 1.1 mm is used. On the inner surface of the second substrate 2 (referred to as the transparent substrate 2), a stripe-shaped ITO transparent electrode 4b is formed, and then a polyimide resin layer having a thickness of 80 nm is applied by printing, baked, and rubbed by a rubbing roll 14. Then, the alignment film 11b was formed. On the other hand, a 100 nm-thick chromium vapor-deposited film is formed on the inner surface of the first substrate 1 (referred to as the transparent substrate 1), and a non-transmissive portion having a width of, for example, about 40 μm is left by photolithography.
After the black matrix layer 5 is formed by etching and removing the pixel portion having an area of 0 μm square or less to form a hole, the hole portion of the chromium vapor deposition film, that is, the pixel portion is covered. A striped R, G, and B color filter layer 8 was formed. Furthermore, thickness 1 on it
A flattening film 10 made of an epoxy resin having a thickness of μm was laminated, and a transparent electrode 4a and an alignment film 11a were formed in the same manner as in the case of the transparent substrate 1.

Further, spacers 3 were formed on the substrate 2 by the method shown in FIG. This method generally includes steps of (a) rubbing the alignment film 11b, (b) applying the photosensitive polymer 3 ', (c) exposing, developing and baking, and (d) printing the seal 6. That is, the alignment film 11 of the substrate 2
After rubbing b, 3, 3 on the alignment film 11b.
Polymerization reaction of 1 mol% of ′ ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 1 mol% of p-phenylenediamine in N-methyl-2-pyrrolidone at 10 ° C. for 6 hours to give a solid content A polyamic acid solution having a content of 10% by weight was synthesized, and BPDA and an equivalent amount of [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine were added to the polyamic acid solution to obtain a liquid photosensitive polymer (polyimide precursor). ) Was generated. The liquid photosensitive polymer 3'is applied by a spin coat method and the temperature is 100 ° C.
After drying for 1 hour, exposing it to the light 15 of a high-pressure mercury lamp through a light-shielding mask, positively developing it in water, and baking it, the thickness and line width of the unexposed part were almost 5 respectively. A polyimide type relief pattern having a thickness of 0.5 μm could be obtained. The spacer 3 may be provided on the alignment film 11a on the substrate 1 side instead of the substrate 2.

The transparent electrodes 4a and 4b formed in stripes on the two transparent substrates 1 and 2 form matrix intersections, and the spacers 3 are arranged so as to be orthogonal to each other so as to overlap the black matrix layer 5. -After printing, the STN type liquid crystal 13 mainly composed of fluorine is injected, and then the injection port 7 provided in the seal 6 is sealed to obtain a STN having a twist angle of 240 degrees.
A liquid crystal display device was produced. As a result, a liquid crystal display device was obtained in which the alignment was good and the display unevenness did not occur.

Example 2 Of the transparent substrates 1 and 2 produced in the same manner as in Example 1, 1 mol% of pyromellitic dianhydride (PMDA) and 2, 2 were formed on the alignment film 11a of the transparent substrate 1. -Bis (4- (p-aminophenoxy) phenyl) propane 0.7 mol%, diaminosiloxane 0.3
Polymerization reaction of mol% in N-methyl-2-pyrrolidone at 5 ° C. for 8 hours to synthesize a polyamic acid solution having a solid content of 10% by weight, and this polyamic acid solution was mixed with PMDA and an equivalent amount of [[(2, Liquid photosensitive polymer to which 6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine is added
(Polyimide siloxane precursor) was produced. The liquid photosensitive polymer is applied by a spin coat method to obtain 100
It was dried at ℃ for 1 hour, exposed with a high-pressure mercury lamp through a light-shielding mask, positively developed in water and baked, and the thickness and line width were 5.0 μm with almost no erosion of the unexposed area.
It was possible to obtain a polyimide siloxane-based release pattern.

The transparent electrodes formed in stripes on the above two transparent substrates form matrix intersections, and the spacers are sandwiched so as to overlap with the black matrix layer so that the spacers are orthogonally arranged. A STN liquid crystal display element having a twist angle of 220 degrees was manufactured by injecting STN type liquid crystal mainly containing the above and then sealing the injection port. As a result, a liquid crystal display device was obtained in which there was no unevenness of orientation and display unevenness did not occur.

Example 3 Of the transparent substrates 1 and 2 produced in the same manner as in Example 1, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was formed on the alignment film 11b of the transparent substrate 2. 1 mol% of (BPDA) and 1 mol% of isophthalic acid dihydrazide in N-methyl-2-pyrrolidone at 15 ° C.
Polymerization reaction is carried out for a time to synthesize a polyhydrazide acid solution having a solid content of 10% by weight, and B is added to the polyhydrazide acid solution.
PDA equivalent to N-[[(2,6-dinitrophenyl)
-1-Methylmethoxy] carbonyl] cyclohexylamine was added to obtain a liquid photosensitive polymer (polyamideimide precursor). This liquid photosensitive polymer was applied by a spin coat method, dried at 100 ° C. for 1 hour, exposed through a light-shielding mask with a high-pressure mercury lamp, positively developed in water, and baked. It was possible to obtain a polyamide-imide type relief pattern having a thickness and a line width of 6.5 μm with almost no erosion of the part.

The transparent electrodes formed in stripes on the above two transparent substrates form matrix intersections, and the spacers are sandwiched so as to overlap with the black matrix layer. A STN liquid crystal display device having a twist angle of 200 degrees was manufactured by injecting an STN type liquid crystal mainly containing the above and then sealing the injection port. As a result, a liquid crystal display device was obtained in which there was no unevenness of orientation and display unevenness did not occur.

[Embodiment 4] In the same manner as in Embodiment 1, the transparent substrates 1 and 2 have a size of 300 × 200 mm and a thickness of 1.1.
After forming an active matrix (TFT) transparent electrode on the transparent substrate 2 using a glass plate having a thickness of 80 mm, a polyimide resin layer having a thickness of 80 nm is printed and applied, and the alignment film 11b is formed by baking and rubbing treatment. Was formed. on the other hand,
A 100 nm-thick chromium vapor deposition film is formed on the transparent substrate 1, and the width is 40 μm, for example, by photolithography.
The non-transmissive portion was left to some extent, and the portion to be a pixel portion having a size of 100 μm square or less was removed by etching so as to form a hole. Next, a striped color filter layer of R, G, and B colors was formed to cover the hole portion of the chromium vapor deposition film, that is, the portion to be the pixel portion. Further, a flattening film made of an epoxy resin having a thickness of 1 μm is laminated thereon, and the transparent electrode 4a and the alignment film 11a are formed in the same manner as in the case of the transparent substrate 2. Then, on the alignment film 11b of the transparent electrode 2, 3, 3 ',
4,4'-biphenyltetracarboxylic dianhydride (BP
DA) and 1 mole% of 2,2-bis (4- (p-aminophenoxyphenyl) hexafluoropropane) equivalent to N-
Polymerization reaction was performed in methyl-2-pyrrolidone at 10 ° C. for 6 hours to synthesize a polyhydrazide acid solution having a solid content of 10% by weight, and BPDA and an equivalent amount of N-[[((2,6 -Dinitrophenyl) -1- (2 ',
6'-Dinitrophenyl) methoxy] carbonyl] cyclohexylamine was added to obtain a liquid photosensitive polymer (polyamideimide precursor). This liquid photosensitive polymer was applied by a spin coat method, dried at 100 ° C. for 1 hour, exposed with a high-pressure mercury lamp through a light-shielding mask, positively developed in water, and baked. It was possible to obtain a polyamide-imide type relief pattern having a thickness and a line width of 6.0 μm with almost no erosion of the part.

The active matrix electrodes and transparent electrodes formed in stripes on the two transparent substrates described above form matrix intersections, and spacers are sandwiched so as to overlap with the black matrix layer and are printed at right angles. After that, a TFT type liquid crystal mainly composed of fluorine was injected, and then the injection port was sealed to manufacture a TFT liquid crystal display element having a twist angle of 90 degrees. As a result, a liquid crystal display device was obtained in which there was no unevenness of orientation and display unevenness did not occur.

[Embodiment 5] 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was formed on the active matrix (TFT) electrodes and the alignment film 11b on the transparent electrode substrate 2 prepared in the same manner as in Embodiment 1. Thing (BTDA) 1 mol%
And m-phenylenediamine were polymerized in N-methyl-2-pyrrolidone at 5 ° C. for 6 hours to synthesize a polyamic acid solution having a solid content of 10% by weight, and BTDA and an equivalent amount of N- were added to the polyamic acid solution. [[(2-Nitrophenyl)-
1- (2'-Nitrophenyl) methoxy] carbonyl] cyclohexylamine was added to produce a liquid photosensitive polymer (polyimide precursor). The liquid photosensitive polymer was applied by a spin coat method, dried at 100 ° C. for 1 hour, exposed through a light-shielding mask with a high pressure mercury lamp, positively developed in water, and baked. As a result, it was possible to obtain a polyimide-based relief pattern having a thickness and a line width of 5.5 .mu.m while hardly eroding the unexposed portion.

The two active matrix electrodes and the transparent electrodes formed in the form of stripes form matrix intersections, and the spacers are sandwiched in a perpendicular arrangement so as to overlap with the black matrix layer. After seal printing, fluorine is used. A TFT-type liquid crystal mainly composed of a system was injected, and the injection port was sealed to manufacture a TFT liquid crystal display device having a twist angle of 90 degrees. As a result, a liquid crystal display device was obtained in which there was no unevenness of orientation and display unevenness did not occur.

[Example 6] 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was formed on the active matrix (TFT) electrodes and the alignment film 11b of the transparent electrode substrate 2 prepared in the same manner as in Example 1. (BPDA) 1 mol% and 1,5-diaminonaphthalene 1 mol% N-methyl-2
-Polymerization reaction was carried out in pyrrolidone at 10 ° C for 6 hours to synthesize a polyamic acid solution having a solid content of 10% by weight. In the polyamic acid solution, BPDA and an equivalent amount of N-[[(2,6-
Dinitrophenyl) -1-methylmethoxy] carbonyl] cyclohexylamine was added to obtain a liquid photosensitive polymer.
(Polyimide precursor) was obtained. This photosensitive polymer was applied by a spin coat method, dried at 100 ° C. for 1 hour, exposed with a high-pressure mercury lamp through a light-shielding mask, positively developed in water, and baked. A polyimide series relief pattern having a thickness and a line width of 5.5 μm could be obtained without eroding.

The active matrix electrodes and transparent electrodes formed in stripes on the above two transparent substrates form matrix intersections, and spacers are sandwiched so as to overlap with the black matrix layer so as to be orthogonally printed. After that, a TFT type liquid crystal mainly composed of fluorine was injected, and then the injection port was sealed to manufacture a TFT liquid crystal display element having a twist angle of 80 degrees. As a result, a liquid crystal display device was obtained in which there was no unevenness of orientation and display unevenness did not occur.

Example 7 1 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was formed on the alignment films of the transparent substrates 1 and 2 prepared in the same manner as in Example 1. 1 mol% of 4,4′-diaminodiphenylmethane was polymerized in N-methyl-2-pyrrolidone at 10 ° C. for 6 hours to synthesize a polyamic acid solution having a solid content of 10% by weight, and BPDA was added to the polyamic acid solution. And an equivalent amount of [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine were added to obtain a photosensitive polymer (polyimide precursor). Spin this photosensitive polymer
Coating, drying at 100 ° C for 1 hour, exposing with a high-pressure mercury lamp through a light-shielding mask, and developing and baking in water, the thickness and line width of the unexposed area were hardly eroded. A polyimide-based relief pattern having a thickness of 6.0 μm could be obtained.

Stripe-shaped transparent electrodes of the above two transparent substrates form matrix intersections, and spacers are formed regardless of the black matrix layer. , STN mainly based on fluorine
After injecting liquid crystal of the mold, the injection port was sealed to prepare an STN liquid crystal display element having a twist angle of 250 degrees. as a result,
A liquid crystal display device was obtained in which there was no unevenness of orientation and display unevenness did not occur.

Comparative Example 1 Of the transparent substrates 1 and 2 produced in the same manner as in Example 1, polymer particles containing divinylbenzene as a main component were mixed with water or alcohol on the alignment film 11b of the transparent substrate 2. Dispersion density of spacers as dispersion medium 10
The substrate was sprayed at 0 to 200 pieces / mm ² , and the substrate was heated on a hot plate at 120 ° C. for 10 minutes. Then, above 2
The transparent electrodes formed in stripes on one transparent substrate form matrix intersections, and the surfaces of the substrates on which the spacers are scattered are opposed to each other. Substrates are stuck together and S mainly composed of fluorine
After injecting the TN type liquid crystal, the injection port was sealed to prepare an STN liquid crystal display element having a twist angle of 240 degrees. As a result, the spacer members aggregated to generate dot-shaped alignment defects, and the spacer members moved during liquid crystal injection to cause display unevenness.

[Comparative Example 2] Spacers of silica particles containing SiO ₂ as a main component were dispersed on the alignment film 11b of the transparent substrate 2 of the transparent substrates 1 and 2 produced in the same manner as in Example 1 at a dispersion density. It was sprayed at 200 to 300 pieces / mm ² , and the substrate was heated on a hot plate at 120 ° C. for 10 minutes. After that, the two transparent substrates are formed into stripe-shaped active matrix electrodes, transparent electrodes form matrix intersections, and the surfaces of the substrates on which the spacers are scattered are made to face each other.
A TFT liquid crystal with a twist angle of 90 degrees is obtained by bonding the upper and lower substrates with a sealant printed on one substrate and injecting a TFT-type liquid crystal mainly composed of fluorine, and then sealing the injection port. A display element was produced. As a result, the spacer members aggregated to generate dot-shaped alignment defects, and the spacer members moved during liquid crystal injection to cause display unevenness.

[Comparative Example 3] JP-A-49-112241 which uses a negative cross-linking reaction on the alignment film 11b of the transparent substrate 2 of the transparent substrates 1 and 2 produced in the same manner as in Example 1 A photosensitive polyamic acid derived from the above pyromellitic acid derivative is applied by a spin coat method,
When dried at ℃ for 1 hour, exposed to a high pressure mercury lamp through a light-shielding mask, negatively developed with an organic solvent, and baked,
Swelling occurred in the exposed area, and the microfabrication treatment of the 5.5 μm release pattern could not be obtained. Further, even when the STN liquid crystal display element was manufactured, the defective alignment occurred.

[0035]

According to the present invention, in a liquid crystal display device in which a liquid crystal is sandwiched between two substrates and a space between the substrates is kept by spacers, the spacers are provided on the alignment control layer formed on the inner surface of each substrate. Since the positive photosensitive polymer that can be developed in water is used as a precursor and the product is fixedly formed, the spacers are provided on the orientation control layer evenly distributed in a highly precise pattern. The space when the liquid crystal is enclosed
It is possible to obtain a liquid crystal display element having uniform alignment and no display unevenness without the movement of the substrate. Finally, display quality and product yield can be greatly improved and cost reduction can be achieved. Further, the contrast ratio can be improved by providing the spacer in the area of the black matrix layer around the pixel portion.

[Brief description of drawings]

FIG. 1 is a plan view of a liquid crystal display element according to an embodiment of the present invention.

FIG. 2 is a sectional view taken along line II-II of FIG.

FIG. 3 is a process drawing showing the method of manufacturing a liquid crystal display element of the present invention.

[Explanation of symbols]

 1 1st board | substrate 2 2nd polarizing plate 3 spacer 4a, 4b electrode 5 black matrix layer 6 seal 7 liquid crystal injection port 8 color filter layer 9a, 9b polarizing plate 10 planarization layer 11a, 11b alignment film 12 phase plate 13 liquid crystal 14 rubbing roll 15 mercury lamp light

Front Page Continuation (72) Inventor Takao Miwa 7-1 Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Yoshiaki Okabe 7-1 Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd., Hitachi Research Laboratory (72) Inventor, Kishiro Iwasaki, 7-1, 1-1, Omika-cho, Hitachi-shi, Ibaraki Hitachi, Ltd. (72) Inventor, Hiroshi Sasaki, Seven, Mika-machi, Hitachi-shi, Ibaraki 1-1-1, Hitachi, Ltd. Hitachi Research Laboratory

Claims (9)

[Claims] 1. A nematic liquid crystal composition sandwiched between a first substrate and a second substrate each having a stripe-shaped electrode and an alignment control layer covering the electrode on the inner surface, and both substrates having the inner surfaces opposed to each other. In a liquid crystal display device having a spacer for maintaining a distance between both substrates, the spacer heats a water-developable positive photosensitive polymer to form an alignment control layer on either the first substrate or the second substrate. A liquid crystal display element comprising a fixed product. 2. A first substrate having a stripe-shaped first electrode and an alignment control layer covering the first electrode on an inner surface thereof,
A stripe-shaped second electrode extending in a direction orthogonal to the first electrode and a second substrate having an alignment control layer covering the second electrode formed on the inner surface, and a nematic sandwiched between the two substrates having the inner surfaces facing each other. In a liquid crystal display device having a liquid crystal composition and a spacer for keeping a space between both substrates, the spacer heats a water-developable positive photosensitive polymer to align the first substrate or the second substrate. A liquid crystal display device comprising a product fixed to a control layer and provided in a region of a black matrix layer around a pixel portion, which is an intersecting portion formed by vertically overlapping a first electrode and a second electrode. . 3. The liquid crystal display device according to claim 1, wherein the photosensitive polymer is a positive type polyimide precursor. 4. The liquid crystal display device according to claim 1, wherein the photosensitive polymer is a positive-type polyimide siloxane precursor. 5. The liquid crystal display element according to claim 1, wherein the photosensitive polymer is a positive type polyamideimide precursor. 6. The photosensitive polymer is represented by the following general formula (I)
5. A base generator as shown in claim 3 is included.
Alternatively, the liquid crystal display device according to item 5. Embedded image 7. The liquid crystal display device according to claim 1, which is a super twist liquid crystal display device. 8. The liquid crystal display element according to claim 1, which is an active matrix liquid crystal display element. 9. A nematic liquid crystal composition sandwiched between a first substrate and a second substrate each having a stripe-shaped electrode and an alignment control layer covering the electrode on the inner surface, and both substrates having the inner surfaces opposed to each other. In the method of manufacturing a liquid crystal display device having a spacer for maintaining a distance between both substrates, the spacer is a water-developable positive photosensitive polymer on the alignment control layer of either the first substrate or the second substrate. Is applied, dried, exposed to light through a light-shielding mask having a predetermined pattern, developed with water, and baked to produce a liquid crystal display device.