JP2003005187A - Liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a display defect caused by so-called burning in a liquid crystal display device. SOLUTION: In the liquid crystal display device having a liquid crystal layer 7, two substrates 2 for the liquid crystal display device holding the liquid crystal layer and an alignment layer 6 on the side of the surface coming in contact with the liquid crystal of the substrate for the liquid crystal display device, the burning can be prevented by making the volumetric resistance value Ra1 of the alignment layer and the volumetric resistance value R1c of the liquid crystal satisfy the desired relational formula 0.98xR1c>=Ra1. The resistance value of the liquid crystal and the resistance value of the alignment layer are adjusted by adding an additive such as an organic matter and by adding conductive fine particles of a metal oxide coated with an organic film, respectively.

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, and more particularly to a so-called display-free liquid crystal display device.

[0002]

2. Description of the Related Art In recent years, as a display device for a TV, a personal computer, a word processor, and other information devices, a thin, lightweight and low power consumption display device using a liquid crystal display device has been widely used.

This liquid crystal display device is roughly classified into a simple matrix drive type and an active drive type according to the driving method. The simple matrix drive type is called a direct drive type or a passive matrix type, in which slit-shaped electrodes are arranged orthogonally on two substrates and a liquid crystal is sandwiched between the electrodes, and the overlapping parts of the upper and lower transparent electrodes are the unit. It becomes a pixel. As a typical display mode, super twisted nematic (ST
N: Super-Twisted Nematic mode or ferroelectric liquid crystal (FLC: Ferroelectric)
ic Liquid Crystal) mode.
Since neither has an active element in the pixel part, ST
In N, a voltage averaging method that uses steep electro-optical characteristics with respect to voltage is used, and in FLC, a large number of lines can be driven by utilizing the memory property of the liquid crystal itself. In STN, the contrast ratio decreases as the number of display lines increases, and it is difficult to obtain a response speed that can support moving images. Therefore, it is possible to drive the status of especially large and high-definition displays such as notebook PCs and monitors. It is being handed over to the mold.

On the other hand, in active driving, the non-linearity of the current-voltage characteristic of the active element is used as a control switch to enable high-speed voltage writing to the pixel when the active element is in the ON state and voltage retention by a high resistance when the active element is in the OFF state. It is a method of displaying by combining functions.

The active driving method is divided into several methods depending on the structure of the active element used. The two-terminal type and the thin film transistor (T
FT: Thin-Film-Transistor) and the like are classified into a three-terminal type. The two-terminal type active element is a diode type or MIM (Metal-type).
There are Insulator-Metal type, ZnO varistor type and the like, and development utilizing the features of simple structure and low cost is under way.

As a three-terminal type active element, Cd
SeTFT, a-Si TFT using amorphous silicon
(Polycrystalline Silicon)
And LCOS (Liq
uid Crystal on Silicon). The three-terminal active element that is most frequently used at present is an a-Si TFT, which is mainly used for notebook PCs, monitors, and TVs. Recently, it has become possible to fabricate high-performance p-Si TFTs and continuous grain boundary crystal Si TFTs by a low-temperature process that can use a glass substrate, and a light valve for a transmissive projector or a small viewfinder by a conventional high-temperature process. In addition to
Applications are expanding to high definition notebook PCs. In addition, LCOS structured light valves and small displays are being actively developed for use as reflective projectors and viewfinders.

As an example of the active drive system, an active element drive liquid crystal display using a TFT will be briefly described. A scan line (Gate Line) and a signal line (Drain Line), which are electrically separated by an insulating layer, are provided on one substrate, and a T line is provided near the intersection.
The pixel electrode connected to the signal wiring via the FT is arranged, and the voltage can be independently written to each pixel electrode via the TFT. In the active driving, in order to stably hold the voltage in which the voltage is written to the pixel, a storage capacitor (Storage Ca connected to the liquid crystal capacitor of the pixel portion is used.
(Pacator) is also required.

By applying a voltage higher than the threshold voltage Vth of the TFT to the gate electrode, the TFT is turned on,
A current flows between the drain and the source to write the signal voltage, the liquid crystal capacitance and the storage capacitance. After that, by returning the gate voltage to Vth or less, the TFT is turned off (high resistance state), and the voltage can be held in the liquid crystal capacitance and the storage capacitance of the pixel portion. When the TFT is in the OFF state, even if a signal voltage is applied to another pixel on the signal line, it is blocked by the high resistance and is not directly affected by the voltage fluctuation on the signal line. A constant voltage can be applied to the liquid crystal.

Since the TFT drive type is a drive system which realizes static drive in which a constant voltage can be always applied to the liquid crystal by an active matrix, there is almost no restriction on the display mode of the liquid crystal. As a result, the T featuring high contrast ratio, high-speed response, wide viewing angle, etc.
N (Twisted Nematic) mode, ECB
(Electrically Controlled
Briefingence) mode, OCB (Opt
ically Controlled Briefri
and IPS (In Plane Switch)
ching), MVA (Multi-domain V)
A combination with many display modes such as an optical alignment mode is used.

[0010]

As described above, the liquid crystal display device is divided into a simple matrix drive type and an active drive type from the viewpoint of the driving method. However, the dielectric anisotropy of the liquid crystal material and the dipole moment are used. It is common in that the direction (director) of the liquid crystal is controlled by applying a voltage from the outside. Therefore, when charged particles are present in the liquid crystal material, the internal electric field of the liquid crystal display device changes with time due to the displacement of the charged particles, which affects the display characteristics of both the simple matrix drive type and the active drive type. . In the TFT liquid crystal display device, which is a typical active drive type, the voltage of the liquid crystal layer must be maintained for a certain period of time after a write signal is applied for a short period of time, and it is necessary to provide electrically high resistance to the TFT by removing charged particles. Required for liquid crystal materials. It is considered that image sticking occurs in a display device for a TFT liquid due to adsorption of impurity ions in the liquid crystal material on the surface of the alignment film.

On the other hand, it is said that the simple matrix drive type does not need a high resistance for the liquid crystal material for TFT because the voltage holding function is not required. However, at the ON-OFF region boundary which appears characteristically in STN. Regarding the image sticking, the relation with the impurity ions in the liquid crystal is considered.

Burn-in is a phenomenon in which the previous display pattern remains even when the screen is switched when the same pattern is continuously displayed on the liquid crystal display device for a long time. This occurs because the DC component is selectively superimposed according to the contrast of the image,
It has been found that removing the impurity ions in the liquid crystal reduces the image sticking. That is, when the same pattern is continuously displayed, the impurities dissociated into ions in the liquid crystal are biased toward the alignment film surface by the driving voltage (for example, electrophoretically), and the charge is accumulated on the alignment film surface.

However, it is industrially difficult to reduce and control the amount of impurity ions in these liquid crystals, and it is difficult to completely remove the impurity ions. As a result, sufficient measures cannot be taken from the viewpoint of prevention of image sticking, which is a major limitation in the design of the liquid crystal display device. On the other hand, the display quality required for liquid crystal display devices has been increasing year by year.

In view of the above background, the present invention is to provide a liquid crystal display device with high productivity in which burn-in is prevented.

[0015]

The liquid crystal display device of the present invention which achieves the above object has the following constitution. That is, (1) In a liquid crystal display device having an alignment film on the side of a surface of the liquid crystal display device substrate in contact with the liquid crystal, the liquid crystal volume is formed between the two liquid crystal display device substrates. A liquid crystal display device characterized by satisfying the relationship of 0.98 × Rlc ≧ Ral, where Rlc is the resistance value and Ral is the volume resistance value of the alignment film.

(2) Liquid crystal is interposed between two liquid crystal display device substrates, and an alignment film is provided on the side of the liquid crystal display device substrate in contact with the liquid crystal. In a liquid crystal display device having an active element and a pixel electrode on the side of the substrate in contact with the liquid crystal, the volume resistance value of the liquid crystal is Rlc, and the volume resistance of the alignment film on the substrate having the active element and the pixel electrode. A liquid crystal display device characterized by satisfying the relationship of 0.98 × Rlc ≧ Ral1, Ral2, where Ral1 is the value and Ral2 is the volume resistance value of the alignment film on the opposing substrate.

(3) The liquid crystal display device as described in (2) above, wherein 0.98 × Rlc ≧ Ral1 ≧ Ral2.

(4) The liquid crystal display device according to any one of (1) to (3), wherein the alignment film contains conductive particles.

(5) One or more of indium oxide, tin oxide, indium tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide and zinc oxide are used as the conductive particles. The liquid crystal display device according to (4).

(6) The liquid crystal display device according to any one of (1) to (3) above, wherein the alignment film contains a metal alkoxide.

(7) The liquid crystal display device according to any one of (1) to (6), wherein the liquid crystal display system is an IPS system.

(8) The liquid crystal display device according to any one of (1) to (6), wherein the liquid crystal display system is a vertical alignment system.

(9) The liquid crystal display device according to any one of (1) to (8), which uses a low temperature polycrystalline silicon TFT or a continuous grain boundary crystalline silicon TFT.

(10) The liquid crystal according to any one of (1) to (9), wherein at least one of the two liquid crystal display device substrates is a color filter substrate having colored pixels. Display device.

(11) The liquid crystal display device as described in (10) above, wherein the color filter substrate has a frame or a black matrix, and the frame or the black matrix is a resin containing a pigment.

(12) The liquid crystal display device as described in (11) above, wherein the pigment constituting the frame or the black matrix is a metal oxide.

(13) The liquid crystal display device according to the above (12), wherein the metal oxide contains at least titanium oxynitride.

In the present invention, such a liquid crystal display device can obtain higher reliability which is improved against burn-in.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystal display device of the present invention comprises a liquid crystal interposed between two substrates for liquid crystal display devices, and has an alignment film on the side of the liquid crystal display device substrate which is in contact with the liquid crystal. ing. The alignment film is an organic thin film for aligning liquid crystal molecules in a predetermined direction.

The liquid crystal display device is not limited by its driving method. The driving method is divided into a simple matrix driving type and an active driving type.

As a simple matrix drive type, STN,
It is preferably used for a display method such as FLC mode. On the other hand, as an active driving type, the active element is a 2-terminal type (diode type, MIM type, ZnO varistor type), 3-terminal type (CdSeTFT, a-SiT).
FT, p-Si TFT, continuous grain boundary Si TFT, LC
OS or the like is preferable. TN (Twisted Nema)
tic) mode, ECB (Electrically)
Controlled Briefing)
Mode, OCB (Optically Control)
led Briefringence), IPS (In
Plane Switching, for example, LCD PDP International 2000 Liquid crystal panel technology text C-4 Digital media compatible Su.
Per IPS TFT liquid crystal panel latest trend), vertical alignment mode (vertical alignment is a display mode in which liquid crystal is aligned almost vertically to the alignment film. There are several vertical alignment modes, for example, MVA ( Mul
ti-domain Vertical Alignment
ent, for example, (1) Alignment control technology in MVA liquid crystal display, P117 EKISHO V
ol. 3 No. 2 1999, (2) SID2000
25.3: An Ultra-high-qualit
y MVA-LCD Using a New Mul
ti-Layer CF ResinSpacer a
nd Black-Matrix, (3) SID2000
23.1: Fast-Switching LCD
with Multi-Domain Vertica
l Alignment Driven by anO
Blique Electric Field, (4) Japanese Patent No. 2947350) mode, PVA (Patt)
ered Vertical Alignment)
Mode, ASV (Advanced Super V)
Such a display method (for example, as a reference, the trend of liquid crystal displays in the 21st century, P408 EKISHO Vo
l. 4 No. 4 2000). In these display modes, (1) a method of providing a resin protrusion for divided orientation, (2) a method of patterning a driving electrode in a zigzag shape or a comb tooth shape to diversify the direction in which a voltage is applied, (3) orientation The orientation of the liquid crystal may be made into a plurality of domains by using a method in which the direction is divided within a pixel by using optical orientation.

The liquid crystal display device of the present invention can be suitably applied to a reflective liquid crystal display device and a transmissive liquid crystal display device, and also to a reflective transmissive liquid crystal display device which has recently been used for a portable information terminal or the like.

Also in these display systems, low temperature p-Si is used.
(That is, low-temperature polycrystalline silicon) TFT (for reference, for example, low-temperature polycrystalline silicon TFT technology and application to liquid crystal panel, P131 EKISHO Vol.
2 2000) and continuous grain boundary crystal Si (silicon) TF
A liquid crystal display device using a T, which is an SRAM (Static
Random Access Memory) is built in the pixel part of the liquid crystal display device substrate, and in the case of a type of display device that does not need to read access data to the peripheral circuit and write to the pixel when displaying a still image, the liquid crystal is always displayed when the still image is displayed. Since a voltage is applied, image sticking is likely to occur, so that the liquid crystal display device having the configuration of the present invention is particularly preferably used. Low-temperature polycrystalline silicon and continuous grain boundary crystals have higher electron mobility than amorphous silicon. The electron mobility of amorphous silicon is 0.5 to ¹ μm ^2.
In contrast to / V · sec, low-temperature poly-polycrystalline silicon and continuous grain boundary crystal silicon have a thickness of 30 μm ² / V · sec or more, further 50 μm ² / V · sec or more. By using low temperature polysilicon or continuous grain boundary crystal silicon,
High aperture ratio, low power consumption, high definition, and system-on-glass are possible.

The relationship between the volume resistance value of the liquid crystal and the volume resistance value of the alignment film is set as follows, so that the charge on the alignment film is less likely to be accumulated and the burn-in prevention capability is enhanced. That is,
When the volume resistance value of the liquid crystal is Rlc and the volume resistance value of the alignment film is Ral, 0.98 × Rlc ≧ Ral is preferable, and 0.90 × Rlc ≧ Ral is further preferable to further reduce image sticking, and further 0 It is preferable that 1 × Rlc ≧ Ral.

In a liquid crystal display device having an active element and a pixel electrode on the side of one of the liquid crystal display device substrates which is in contact with the liquid crystal, the volume resistance value of the liquid crystal is Rl.
When the volume resistance value of the alignment film on the substrate having the active element and the pixel electrode is Ral1 and the volume resistance value of the alignment film on the opposing substrate is Ral2, 0.98 × Rlc ≧ Ra
l1 and Ral2 are preferable, and 0.90 × Rlc ≧ Ral1 and Ral2 are preferable to further reduce image sticking, and further 0.1 × Rlc ≧ Ral1 and Ral2 are preferable.

On the other hand, if the volume resistance of the alignment film is too low,
It may be difficult to apply a voltage only to a specific pixel, and the display quality may deteriorate. The volume resistance of the alignment film is 1
It is preferably 0 ⁶ Ω · cm or more, more preferably 10 ⁷ Ω.
-Cm or more, most preferably 10 ⁸ Ω-cm or more. Especially in a liquid crystal display device using a low temperature polycrystal silicon TFT or a continuous grain boundary crystal silicon TFT, the alignment film causes a stray capacitance of a drive circuit formed on the liquid crystal display device substrate, which may cause a malfunction. There is 10 ⁸ Ω
・ It is preferably cm or more.

The volume resistance value of the liquid crystal is not particularly limited,
In order to obtain good display quality, 10 ⁸ Ω · cm or more is preferable, and in industrial production of liquid crystal, 10 ¹⁹ Ω · cm.
-It is preferably not more than cm. Therefore, 10 ⁸ Ω · cm
Ral1 and Ral2 between 10 ¹⁹ Ω · cm are preferred.

Further, particularly in an alignment film formed on a substrate for a liquid crystal display device having an active element and a pixel electrode, the display quality may be deteriorated when the resistance value of the alignment film is low. Therefore, in a liquid crystal display device having an active element and a pixel electrode on the side of one of the liquid crystal display device substrates that comes into contact with the liquid crystal, the design margin for printing is maintained and the resistance value of the alignment film is too low. In order to maintain a margin with respect to, a volume resistance value of the alignment film on the substrate having the active element and the pixel electrode is Ral1, and a volume resistance value of the alignment film on the opposing substrate is Ral2. It is preferable that ≧ Ral2. Therefore, 0.98 × Rlc ≧ Ral1 ≧ Ral2 is preferable, and 0.90 × is required to further reduce image sticking.
Rlc ≧ Ral1 ≧ Ral2 is preferable, and further 0.1 × Rlc
≧ Ral1 ≧ Ral2 is preferable.

The volume resistance value (ρ) of the alignment film is measured by a three-terminal method with a guard ring by a voltage (electrode area (S), film thickness (d) of the alignment film) above and below the alignment film. V) is applied, and it is calculated from the flowing current (I) using the following equation.

Ρ = (V / I) · (d / S) The measured ρ is defined as Ral or Ral1 or Ral2.

The volume resistance value (ρ) of the liquid crystal is measured on the electrode surfaces provided above and below the cell (electrode area (S), gap (d) of the liquid crystal layer) filled with liquid crystal by the three-terminal method with a guard ring. A voltage (V) is applied, and from the flowing current (I),
It is calculated using the following formula.

Ρ = (V / I) · (d / S) Let ρ be the measured ρ.

The surface resistance of the alignment film is preferably 10 ⁷ to 10 ¹⁴ Ω / □. In the case of a low resistance material, the surface resistance value decreases as the film thickness of the material increases, but in the case of the alignment film of the present invention, the film resistance does not necessarily change linearly because the resistance value is high. The surface resistance value is measured according to JIS K6911 using a ring electrode.
Depending on the resistance of the alignment film to be measured in a simple manner, using a surface resistance measuring device “Loresta” or “Hiresta” manufactured by Mitsubishi Petrochemical Co., Ltd., a four-point probe method or a two-terminal method using a ring electrode The surface resistance value (sheet resistance) can be measured by the three-terminal method.

The substrate used in the present invention is not particularly limited, but inorganic glass such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silica, a plastic film or A transparent substrate such as a sheet is preferably used. A liquid crystal display device is configured by using a substrate for a liquid crystal display device in which colored layers such as red, blue and green, driving electrodes, and a light shielding film are formed on the substrate as necessary.

As the liquid crystal used in the liquid crystal display device,
It can be appropriately selected depending on the relationship with the volume resistance value of the alignment film. Further, the liquid crystal is selected according to the display method and the driving method. For example, nematic liquid crystals and smectic liquid crystals are used to obtain good display. Smectic liquid crystals include ferroelectric liquid crystals, antiferroelectric liquid crystals, thresholdless antiferroelectric liquid crystals, and the like. As the nematic liquid crystal, those having a positive or negative dielectric anisotropy can be appropriately used depending on the display system.

The resistance value can be adjusted by appropriately adding additives to the liquid crystal. For example, 4-cyano-3-fluorophenyl-trans-4-ethylphenylcarboxylate, 1- [4- (3,4,5-trifluorophenyl) cyclohexyl] -2- (4-methylcyclohexyl) ethane, 4 -Cyano-3-fluorophenyl-
4- (4-propylcyclohexyl) phenylcarboxylate, 3,4-dicyano-5-fluorophenyl-
Trans-4-propylcyclohexylcarboxylate, 3,4-dicyano-5-fluorophenyl-trans-4-propylcyclohexylcarboxylate, 3
-Cyano-4-trifluoromethoxy-5-fluorophenyl-trans-4-ethylcyclohexylcarboxylate, 3-cyano-2-fluorophenyl-trans-4-pentylcyclohexylcarboxylate, 2
-(Trans-4-propylcyclohexyl) -1-
[Trans-4- (2,3-dicyanophenyl) cyclohexyl] ethane or the like can be used.

The alignment film is a film formed on the side of the liquid crystal display device substrate that is in contact with the liquid crystal, and has the property of aligning the liquid crystal in a predetermined direction (director).

As a material for the alignment film, a photosensitive or non-photosensitive material such as a polyimide resin, a polyamide resin, or a polyvinyl alcohol resin is preferably used, but the material is not limited to these. However, a polyimide resin is preferable from the viewpoint of heat resistance and reliability of the alignment film.

The polyimide resin can be obtained by forming a soluble polyimide type alignment film solution or a polyamic acid type alignment film solution on a substrate for a liquid crystal display device, and then, if necessary, drying, firing or light irradiation. The alignment film material is formed on the substrate by flexographic printing, spin coating, roll coating, slit die coating, silk printing, or the like on the substrate for liquid crystal display device.

The polyimide resin preferably used as the alignment film is not particularly limited, but usually, a polyamic acid containing a structural unit represented by the following general formula (1) as a main component is heated or appropriately heated. Those imidized with a catalyst are preferably used.

[0051]

[Chemical 1]

Here, n in the general formula (1) is a number of 1 to 2. R ₁ is an acid component residue, and R ₁ Is at least 2
Represents a trivalent or tetravalent organic group having 4 carbon atoms.
From the viewpoint of heat resistance, R ₁ Is preferably a trivalent or tetravalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms. R ₁ Examples of phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, cyclobutyl group, cyclopentyl group, etc. Groups, but are not limited to.

R ₂ represents a divalent organic group having at least 2 carbon atoms. From the viewpoint of heat resistance, R ₂ is preferably a divalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms. As an example of R ₂ ,
Examples include groups derived from phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, diphenylmethane group, cyclohexylmethane group, etc. However, the present invention is not limited to these. In the polymer having the structural unit represented by the general formula (1) as a main component, R ₁ and R ₂ may each be composed of one of them, or may be composed of two or more kinds of copolymers. It may be a united body.

In order to implement the constitution of the liquid crystal display device of the present invention, a commercially available alignment film may be used. For example,
Nissan Chemical SE-130, SE-150, SE-2
110, SE-410, SE-610, SE-118
0, SE-2170, SE-1211, SE-314
0, SE-3210, SE-3310, SE-351
0, SE-5291, SE-6210, SE-749
2, SE-7992, SE-7511L, SE-819
2L, RN-1322, RN-1332, RN-134
9, RN-1358, RN-1386, RN-141
7, RN-1436, RN-1450, RN-1477
And PIA-5140 and PIA-515 manufactured by Chisso Corporation
0, PIA-5310, PIA-X322, PIA-2
024, PIA-2700, PIA-2800, PIA
-2900 AL1000, AL manufactured by JSR
1068, AL1072, AL1077, AL1F0
0, AL3000, AL4000, AL5000, AL
6000, AL7000, AL8000, JALS-1
46, JALS-212, JALS-246, JALS
-406, JALS-445, JALS-469, JA
LS-550, JALS-552, JALS-553,
JALS-555, JALS-556, JALS-56
6, JALS-725, JALS-1082, JAL
S-1085, JALS-1216 or the like may be used alone, or two or more of them may be mixed and used, or other polymer component may be appropriately added.
The resin components contained in these products may be appropriately selected and used.

The alignment film of the present invention may contain conductive particles in order to adjust the resistance value of the alignment film.
As the conductive particles added to the alignment film, indium oxide,
Tin oxide, zinc oxide, cadmium oxide, indium tin oxide, antimony pentoxide-doped tin oxide, fluorine-doped tin oxide, phosphorus-doped tin oxide, aluminum-doped zinc oxide,
Gallium-doped zinc oxide, indium-doped zinc oxide,
Cadmium-doped tin oxide and zinc-doped cadmium,
Examples include tin oxide-doped indium oxide, antimony pentoxide, zinc antimonate, titanium oxide, titanium dioxide, aluminum oxide, zinc oxide, ruthenium oxide, rhenium oxide, silver oxide, nickel oxide, copper oxide, nickel and gold. The particles are not particularly limited thereto, and any particles having conductivity can be used. Moreover, you may use 1 type or multiple types of these particles.
The surface of a resin such as acrylic may be coated with these metals. Among these, tin oxide (NESA) doped with a small amount of antimony pentoxide and indium oxide (ITO) having a small amount of tin oxide dissolved therein are preferable from the viewpoint of exhibiting stable conductivity. From the viewpoints of versatility, economy and availability, ITO is more preferable. The particle size of the conductive particles added to the alignment film is preferably 5 to 50 nm, more preferably 5 to 20 nm, and most preferably 5 to 10 nm.
nm is preferred.

The conductive particles added to the alignment film are preferably achromatic particles. The orientation film to which the conductive particles are added has a chromaticity coordinate (x, y) in the XYZ color system of transmitted light and / or reflected light of the orientation film in the C light source, the F10 light source, or the D65 light source, Degree coordinate (x
0, y0), (x−x0) ² + (y−y0) ² ≦
0.01 is preferable. As a colorimetric method of the transmitted light and the reflected light, there is a method of measuring the transmittance and the reflectance with a microspectrophotometer. From these spectra C source or F10
The stimulus values X, Y, Z in the light source are calculated, and the chromaticity coordinates are obtained. A commercially available microspectroscope, such as Otsuka Electronics M
These calculation programs are incorporated in the CPD-2000.

The conductive particles added to the alignment film are preferably transparent. In order to improve the transparency of the alignment film, it is preferable to further reduce the difference in the refractive index between the resin component forming the alignment film and the conductive particles. In addition, the refractive index of the alignment film can be adjusted by the conductive particles and the metal alkoxide added to the alignment film, and the reflectance and the transmittance of the alignment film can be set to desired values. That is, it is possible to design as an optical multilayer film in consideration of the liquid crystal that comes into contact with the alignment film and the refractive index of the liquid crystal display device substrate.

As the method of adding the conductive particles to the alignment film, (a) the method of directly adding the powder to the resin solution,
(B) Although there is a method of using an ultrafine particle sol in which ultrafine particles are dispersed in a solvent, (b) is preferable from the viewpoint of dispersion stabilization. In the case of (a), for the purpose of stabilizing the dispersion, a dispersion solvent or a dispersant may be added or the particle surface may be coated with silica or an organic film. When the concentration in the alignment film resin is high, it can be covered with an organic film to stabilize the dispersion in the alignment film solution so that the conductive particles do not settle.

As a dispersion solvent for the conductive particles, water, ethanol, methanol, isobutanol, 3-methyl-3 are used.
-Alcohols such as methoxybutanol, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethers such as diethylene glycol diethyl ether, ethyl acetate, N-Butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate Chromatography ether acetate, .gamma.-butyrolactone, esters such as N- methylpyrrolidone, N, N
Amides such as dimethylformamide and N, N-dimethylacetamide, pyrrolidones such as 2-pyrrolidone, and butylcellosolve can be used. Further, in view of the storage stability of the alignment film solution, the dispersion solvent of the conductive particles preferably contains the same solvent as that used for the alignment film.

Further, the resistance value of the alignment film may be adjusted by using a metal alkoxide. Addition of metal alkoxide
This is an effective means for adjusting the electric resistance value, and a conductive substance can be chemically dispersed. It is known that metal alkoxides other than silicon-based alkoxides produce a hydrolyzate in the presence of water or alcohol and an acidic catalyst, and are polymerized by a condensation reaction. Therefore, in a system containing water or an acidic catalyst, the storage stability of the coating liquid may deteriorate. However, since the metal complex formed by the reaction of the β-diketone or β-keto acid ester and the metal alkoxide can suppress the hydrolysis and condensation reactions, the storage stability can be improved. Therefore, when adding a metal alkoxide, it is important to select either a method of directly adding the metal alkoxide or a method of adding the metal alkoxide after converting it into a metal complex, depending on the resin and solvent used. is there. Specific examples of β-diketone and β-keto acid esters include acetylacetone, benzoylacetone, dibenzoylmethane, methylacetoacetate,
Ethyl acetoacetate, benzoyl acetoacetate, ethyl benzoyl acetate, methyl benzoyl acetate and the like can be used.

The metal alkoxide of the present invention includes Mm
It is expressed as (OR) n. Here, m and n are positive integers of 1 or more. The M is not particularly limited, but In, S
N, Zn, Cd and the like are preferable. R is a hydrocarbon group or a halogenated hydrocarbon group.

Specific examples of the metal alkoxide include In
(OCH (CH₃)₂)₃, Sn (OCH (CH₃)₂)_Four,
Zn (OCH (CH₃)₂)₂, Cd (OCH (C
H₃)₂)₂, In (OCH₂CH₂CH₂CH₃)₃, Sn
(OCH₂CH₂CH₂CH₃)_Four, Zn (OCH₂CH₂C
H₂CH₃)₂, Cd (OCH₂CH₂CH₂CH₃)₂, In
(OC ₂H_Five)₃, Sn (OC₂H_Five)_Four, Zn (OC₂H_Five)
₂, Cd (OC₂H_Five)₂, And the like are preferable. High conductivity, pan
In terms of usability and availability, In, Sn, Zn, Cd, etc.
It is preferable to use the metal alkoxide used. A small amount
Tin oxide (NESA) doped with antimony pentoxide and
And indium oxide (ITO) containing a small amount of tin oxide as a solid solution
For the preparation of complex oxides such as copper and cadmium-doped tin oxide
Is the equivalent ratio of two kinds of metal alkoxide
It can be produced by a method of adding soybeans. For use in the present invention
Β-diketones and β-keto acid esters and metals
Specific examples of metal complexes formed by the reaction of alkoxides
Indium acetylacetonate, indium benzene
Zoyl acetonate, indium acetyl acetate,
Tin acetylacetonate, tin benzoylacetonate,
Tin acetyl acetate, zinc acetylacetonate, sub
Lead benzoylacetonate, zinc acetylacetate,
Cadmium acetylacetonate, cadmium benzoi
Luacetonate, cadmium acetylacetate, etc.
Can be mentioned. When problems such as storage stability do not occur
As for, the metal alkoxide alone may be directly added.
Stable electrical properties are obtained by using metal alkoxide
You can

In the alignment film of the present invention, the content of the conductive particles is such that the resin component of the resin composition of the alignment film is 100%.
It is preferably 400 parts by weight or less with respect to parts by weight. If the content of the conductive particles is larger than this, the alignment characteristics of the liquid crystal may be deteriorated.

The thickness of the alignment film of the present invention is 0.001 to 2
μm is preferred. When the film thickness of the alignment film is large, the voltage loss due to the alignment film becomes large, which is not preferable from the viewpoint of driving the liquid crystal display device. The thickness of the alignment film is 0.001 μm
The thinner it is, the more significantly the ability to orient the liquid crystals decreases.

In order to improve the coatability of the alignment film, a surfactant may be added to the resin composition of the alignment film. The amount of such a surfactant added is preferably 10 parts by weight or less, more preferably 1 part by weight or less, relative to 100 parts by weight of the resin.

Specific examples of such a surfactant include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, alkyl, fluorine-modified silicone oil, polyether, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone. Modified silicone oils such as oil, phenol, carboxy, mercapto-modified silicone oil, anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as lauryl trimethyl ammonium chloride, lauryl Amphoteric surfactants such as dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene Uri ether, polyoxyethylene stearyl ether, etc. can be used nonionic surfactants such as sorbitan monostearate.
These surfactants can be used alone or in combination of two or more. Such a surfactant may be added at any time before or after the conductive particles or the metal alkoxide is added.

As the solvent used for the alignment film solution,
Water, alcohols such as ethanol, methanol, isobutanol, 3-methyl-3-methoxybutanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol Ethers such as diethyl ether and diethylene glycol diethyl ether, ethyl acetate, n-butyl acetate,
3-Methoxy-3-methylbutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Esters such as ether acetate and γ-butyrolactone, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, 2
-Pyrrolidones, pyrrolidones such as N-methylpyrrolidone, butyl cellosolve and the like can be used.

A color filter may be used as the liquid crystal display device substrate of the present invention.

The color filter is a substrate having a colored layer of three primary colors forming a pixel at a position corresponding to an opening of the liquid crystal display device, and if necessary, a black matrix, a frame, a transparent protective film and a transparent conductive film.

The black matrix and the frame may be formed of a metal such as chromium or nickel or an oxide thereof, but it is necessary to form a resin black matrix layer composed of a resin and a light-shielding agent for manufacturing cost and waste treatment. It is preferable in terms of cost. Further, the resin black matrix layer can be formed with a thickness in the range of 0.5 μm to 2.0 μm while maintaining the light-shielding performance that does not cause a problem in the display of the liquid crystal display device.

The alignment film and liquid crystal of the present invention are particularly preferably used when having a color filter using a resin light-shielding layer composed of a resin and a light-shielding agent. The resin light-shielding layer has a higher resistance value than that of a black matrix or a frame which is usually formed of a metal or an oxide thereof, a charge is easily accumulated on the substrate, and a display defect is likely to occur. Therefore, it is preferable to use the liquid crystal or liquid crystal alignment film of the present invention in a liquid crystal display device having a black matrix or a frame formed of a resin light shielding layer.

The resin used for the resin light-shielding layer is not particularly limited, but an epoxy resin, an acrylic resin,
Photosensitive or non-photosensitive materials such as urethane type resin, polyester type resin, polyimide type resin, polyolefin type resin and gelatin are preferably used. The resin for the resin light-shielding layer is preferably a resin having higher heat resistance than the resin used for the colored layer or the protective film of the color filter,
A polyimide resin is particularly preferably used because a resin having resistance to an organic solvent used in a step after forming a black matrix or a frame is preferable.

The polyimide-based resin is not particularly limited, but a polyimide precursor (n = 1 to 2) containing a structural unit represented by the following general formula (1) as a main component is usually heated or heated with a suitable catalyst. An imidized product is preferably used.

[0074]

[Chemical 2]

In addition to the imide bond, the polyimide resin may contain a bond other than the imide bond such as an amide bond, a sulfone bond, an ether bond and a carbonyl bond.

In the general formula (1), R ₁ is at least 2
It is a trivalent or tetravalent organic group having one or more carbon atoms. From the viewpoint of heat resistance, R ₁ contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle, and has 3 to 30 carbon atoms.
A valent or tetravalent group is preferred.

Examples of R ₁ are phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenyl sulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, cyclobutyl group, cyclopentyl group. However, the present invention is not limited to these.

R ₂ is a divalent organic group having at least 2 carbon atoms, but from the viewpoint of heat resistance, R ₂ contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle, and A divalent group having 6 to 30 carbon atoms is preferable. Examples of R ₂ include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenyl sulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoropropane group, a diphenylmethane group and a dicyclohexylmethane group. Examples include, but are not limited to: In the polymer having the structural unit (1) as a main component, R ₁ and R ₂ may each be composed of one type, or may be a copolymer composed of two or more types. . Further, in order to improve the adhesiveness with the substrate, it is preferable to copolymerize bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure as a diamine component within a range that does not lower the heat resistance.

Specific examples of the polymer containing the structural unit (1) as a main component include pyromellitic dianhydride, 3,3
′, 4,4′-Benzophenonetetracarboxylic dianhydride 3,3 ′, 4,4′-biphenyltrifluoropropanetetracarboxylic dianhydride 3,3 ′, 4,4′-
Biphenyl sulfone tetracarboxylic acid dianhydride 3,3,3
Paraphenylene and one or more carboxylic acid dianhydrides selected from the group consisting of ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,5, -tricarboxycyclopentyl acetic acid dianhydride, and the like. Diamine, 3, 3
'-Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4
Examples include polyimide precursors synthesized from one or more diamines selected from the group consisting of ′ -diaminodiphenyl sulfone, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenymethane, and the like. Not limited. These polyimide precursors are synthesized by a known method, that is, by selectively combining tetracarboxylic dianhydride and diamine and reacting them in a solvent.

As the light-shielding agent for the resin light-shielding layer, metal oxide powder such as carbon black, titanium oxide, titanium oxynitride, iron tetroxide, etc., metal sulfide powder, metal powder, pigment or a mixture thereof is used. You can Among these, carbon black and titanium oxynitride are particularly preferable because they have excellent light-shielding properties. Since carbon black having a good dispersion and a small particle size mainly exhibits a brownish color tone, it is preferable to mix a pigment having a complementary color with the carbon black to make it an achromatic color.

Titanium oxynitride and titanium oxide have higher volume resistance values than carbon black. When the resistance value of the black matrix or the frame becomes high, it becomes difficult for the electric charge to leak to the alignment film, which is likely to cause burn-in. Therefore,
The liquid crystal and alignment film of the present invention are particularly suitably used for a liquid crystal display device having a color filter using titanium oxynitride or titanium oxide as a light shielding agent for a resin light shielding layer.

The titanium oxynitride and titanium oxide used in the present invention are manufactured by the following methods, but the invention is not limited thereto. (1) A method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (JP-A-49-5432). (2) A method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen (JP-A-57-205322). (3) A method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP-A-60-65069 and JP-A-61-201610). (4) A method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610).

The resin used for the resin black matrix is not particularly limited, but it is a photosensitive or non-photosensitive resin such as epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, gelatin or the like. A material having sexuality is preferably used.
The resin for the black matrix is preferably a resin having higher heat resistance than the resin used for the colored layer of the color filter or the protective film, and the resin having resistance to the organic solvent used in the step after forming the black matrix is preferable. Therefore, a polyimide resin is particularly preferably used.

Further, the black matrix and the frame may be produced by stacking colored layers forming pixels. Since the portion where the colored layers are stacked has a light-shielding property, the liquid crystal panel body in which the need for the black light-shielding film is not relatively high, particularly the normally black type liquid crystal panel body, particularly the reflective liquid crystal display device and the reflection type It is suitable for a transmissive liquid crystal display device.
A black matrix or a frame may be manufactured by stacking two colors of the colored layers forming the pixel, or three colors of the colored layers may be stacked.

The colored layer forming the pixel has a higher resistance value than the resin light-shielding layer in which carbon black is dispersed. Therefore, the liquid crystal and alignment film of the present invention are particularly preferably used for a liquid crystal display device having a color filter using a colored layer in a frame or a black matrix.

Regarding the substrate constituting the liquid crystal display device of the present invention, the color filter substrate will be described in more detail below.

The color filter comprises a colored layer of three primary colors forming a pixel and a transparent conductive film at a position corresponding to the opening of the liquid crystal display device, a black matrix or a frame as necessary,
It is a substrate having a transparent protective film.

The colored layer forming the pixel is generally made of an organic film, and polyimide resin, acrylic resin, epoxy resin or the like is preferably used as the resin component. Pixels are formed by using colorants such as pigments and dyes in these resins. The pigments and dyes can be used in combination as appropriate for expressing the three primary colors. Examples of pigments that can be used include pigments and dyes such as red, orange, yellow, green, blue and purple.

The three primary colors of red (R), green (G) and blue (B) are selected for the colored layer forming the pixel. In general, an element including these three primary colors can be regarded as a unit to form a color display picture element. A resin colored with a colorant is used for the colored layer.

As the colorant used in the colored layer, organic pigments, inorganic pigments, dyes and the like can be preferably used, and various additives such as an ultraviolet absorber and a dispersant may be added. . A wide variety of dispersants such as surfactants, pigment intermediates, dye intermediates, and polymeric dispersants are used. Further, various additives may be added in order to improve coating properties and leveling properties.

Specific examples of the pigment include Pigment Red (PR-) 2, 3, 9, 22, 38,
81, 97, 122, 123, 144, 146, 14
9, 166, 168, 169, 177, 179, 18
0, 190, 192, 206, 207, 209, 21
5, 216, 224, 242, 254, 266, Pigment Green (PG-) 7, 10, 36, 37,
38, 47, Pigment Blue (PB-) 15 (15: 1, 15:
2, 15: 3, 15: 4, 15: 6), 16, 17, 2
1, 22, 60, 64, Pigment Yellow (PY-) 12, 13, 14, 1
7, 20, 24, 83, 86, 93, 94, 95, 10
9, 110, 117, 125, 129, 137, 13
8, 139, 147, 148, 150, 153, 15
4, 155, 166, 173, 180, 185, Pigment Violet (PV-) 19, 23, 29,
30, 32, 33, 36, 37, 38, 40, 50, Pigment Orange (PO-) 5, 13, 17, 31,
36, 38, 40, 42, 43, 51, 55, 59, 6
1, 64, 65, 71, and the like. These pigments may be used alone or in combination of two or more.

The above-mentioned pigment may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment and pigment derivative treatment, if necessary. In addition, PR (Pigment Red), P
G (Pigment Green), PB (Pigment Blue)
Are color indexes (C.I .; The Society of
Dyers and Colorrists Inc.), the official form is C. I. With a suffix (for example, CIPR2
54). It defines dyes and dyeing standards, and each symbol also designates a specific standard dye and its color. In the following description of the present invention, the above C. I. Is omitted (for example,
C. I. If it is PR254, PR254) is performed.

The transparent electrode is usually made of indium tin oxide (ITO), zinc oxide, tin oxide, or the alloy thereof, and in view of these, IT
O is preferred. The transparent electrode is necessary for driving the liquid crystal, but in a liquid crystal display device of a horizontal electric field driving display system (IPS mode), the transparent electrode for driving is on the side of the surface in contact with the alignment film of the color filter. Is not necessary,
Color filters without transparent electrodes are used. The transparent electrode is produced by a method such as a dipping method, a chemical vapor deposition method, a vacuum vapor deposition method, a sputtering method and an ion plating method, but the sputtering method is preferable in order to obtain an electrode with high uniformity. Of these, DC magnetron sputtering is more preferable because a high film formation rate can be obtained, but the present invention is not limited thereto.

A transparent protective film may be provided between the transparent conductive film and the colored layer.

As the transparent protective film, an epoxy resin, an acrylic resin or a polyimide resin can be appropriately used. The refractive index of the transparent protective film is not particularly limited as long as it is different from that of the transparent counter electrode.

In a vertical alignment mode liquid crystal display device, projections for alignment division may be formed on the color filter substrate as occasion demands. It is preferable that the alignment division projections are patterned by using a resin film after forming ITO.
It is preferable to form the projections for alignment division after forming ITO, and then to form the alignment film.

The thickness (cell gap) of the liquid crystal layer of the liquid crystal display device is maintained by using a spacer. Spacers or spherical polymer beads may be dispersed between the substrates to maintain the substrate spacing, or columns may be formed on at least one of the substrates for the liquid crystal display device using photolithography or the like. A method of holding the gap between the substrates by forming them may be used. The alignment film may be formed after the columnar material is formed or before the columnar material is formed.

As a specific example of a substrate having an active element, an example of a method of manufacturing a substrate having a thin film transistor element will be shown below.

A chromium thin film is formed on an alkali-free glass substrate by sputtering, and the gate electrode is patterned by photolithography. Next, plasma CVD
Thus, a silicon nitride film, an amorphous silicon film as an insulating film and a silicon nitride film as an etching stopper are continuously formed. Next, the silicon nitride film of the etching stopper is patterned by photolithography. An n + amorphous silicon film was formed and patterned so that the TFT terminal could make ohmic contact with the metal electrode. At this time, the amorphous silicon film of the channel layer was also patterned at the same time. Further, an ITO film to be a display electrode is formed and patterned. Further, aluminum is deposited as a wiring material by sputtering, and a signal wiring and a metal electrode of the TFT are manufactured by photolithography. Using the drain electrode and the source electrode as a mask, the n + amorphous silicon film in the channel portion is removed by etching to obtain an electrode substrate having a TFT element. In the case of a reflective liquid crystal display element, the display electrode is made of a material having high reflectance such as aluminum or silver.

Next, the liquid crystal display device will be described. A substrate for a liquid crystal display device (color filter) on which a colored layer and a black matrix layer are formed and a substrate for a liquid crystal display device facing each other are attached to each other. In addition to the auxiliary capacitance and the pixel electrode, a thin film transistor (TFT) element, a gate electrode, a signal line, and the like are provided on the substrate for the liquid crystal display device facing the color filter. An alignment film is provided on the pair of substrates for a liquid crystal display device, and an alignment process such as rubbing is performed. After the alignment treatment, the color filter and the counter substrate are attached to each other using a sealant, and liquid crystal is injected through the injection port provided in the seal portion, and then the injection port is sealed. The liquid crystal display device is completed by attaching the polarizing plate to the outside of the substrate and then mounting an IC driver or the like.

The liquid crystal display device of the present invention is used for light valves for notebook PCs, monitors, TVs, projectors, small viewfinders, mobile phones, personal digital assistants, and the like.

[0102]

EXAMPLES The present invention will now be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A liquid crystal display device of the in-plane switching (IPS) system was used. [Production of Liquid Crystal Display Device] Two transparent glass substrates (2) having a thickness of 0.7 mm and having a polished surface are used as substrates. (Preparation of substrate having active element and pixel electrode)
A thin film transistor, a pixel electrode (5) and the like were formed on one of the two glass substrates to obtain a liquid crystal display device substrate for active driving. The structure of this TFT array is a lateral electric field (IPS) type structure, and includes a slit-shaped common electrode (also referred to as a common electrode) (12) and a pixel electrode (5).
Are formed in the opening region. By using this electrode, a voltage can be applied in parallel to the glass substrate between the common electrode and the pixel electrode. (Production of Color Filter Substrate) A color filter was formed on the substrate facing the active driving liquid crystal display substrate. <Preparation of resin black matrix> γ-butyrolactone 16644.1 g, 4,4′-in a 20 L reaction kettle equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device with hot / cooling water, and a stirrer. 600.7 g of diaminodiphenyl ether, 670.2 g of 3,3′-diaminodiphenylsulfone, and 74.6 g of bis-3- (aminopropyl) tetramethylsiloxane were added, and the kettle was heated to 30 ° C. After 30 minutes, 3,3 ', 4,4'-
Benzophenone tetracarboxylic dianhydride 644.4
g, pyromellitic dianhydride 641.3 g, 3,
294.2 g of 3 ', 4,4'-biphenyltetracarboxylic dianhydride was added and the kettle was heated to 58 ° C. After 3 hours, 11.8 g of maleic anhydride was added, and the mixture was heated at 58 ° C. for another hour to give N of polyamic acid.
An MP solution (B1) was obtained.

Carbon black (4.6 g), polyamic acid solution (B1) (24.0 g) and N-methylpyrrolidone (61.4 g) were dispersed together with glass beads (90 g) using a homogenizer at 7,000 rpm for 30 minutes, and then dispersed.
The glass beads were removed by filtration to obtain a carbon black mill base.

Pigment Blue 15: 6 2.2
g, polyamic acid solution (A1) 24.0 g, N-methylpyrrolidone 63.8 g together with glass beads 90 g using a homogenizer, after the dispersion treatment at 7,000 rpm for 30 minutes, the glass beads were removed by filtration to obtain a blue pigment mill base. .

By mixing all the obtained mill bases, a resin black matrix paste was obtained.

A resin black matrix paste was spin-coated on a glass substrate and heated at 50 ° C. for 10 minutes at 90 ° C.
10 minutes at 110 ° C. for 20 minutes in an oven using an oven, and dried in air to obtain a polyimide precursor colored film having a thickness of 1.1 μm. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on this film and dried by heating at 80 ° C. for 20 minutes to obtain a resist film having a film thickness of 1 μm. Using a UV exposure machine PLA-501F manufactured by Canon Inc., the intensity at a wavelength of 365 nm is 5 through a photomask made of chromium.
It was irradiated with ultraviolet rays of 0 mJ / cm ² . 2.38 wt% of tetramethylammonium hydroxide after exposure
The photoresist and the polyimide precursor colored coating film were developed at the same time by immersing in a developing solution consisting of the above aqueous solution. After etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. Further, the polyimide precursor colored film thus obtained was applied in a nitrogen atmosphere for 3 hours.
A heat treatment was carried out at 00 ° C. for 30 minutes to obtain a polyimide colored pattern coating film having a film thickness of 0.9 μm, which was composed of lattice-shaped pixel portions and a frame portion surrounding them. <Formation of Colored Layer and Transparent Protective Film> Pigment Red 177, Pigment Green 36, and Pigment Blue 15: 6 are prepared as red, green, and blue pigments, respectively, and mixed and dispersed with a polyamic acid solution (P1) to obtain red. Three kinds of colored pastes of blue, green and green were obtained.

The obtained red paste was spin-coated on a resin black matrix substrate, and the mixture was heated at 50 ° C. for 10 minutes for 90 minutes.
The polyimide precursor colored film having a thickness of 1.2 μm was obtained by heating and drying in air using an oven at 10 ° C. for 10 minutes and 110 ° C. for 20 minutes. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto this film, and the photoresist is applied at 80 ° C. for 20 minutes.
After heating and drying for 1 minute, a resist film having a film thickness of 1.1 μm was obtained. Using a UV exposure machine PLA-501F manufactured by Canon Inc., a wavelength of 365 nm through a chrome photomask.
UV light having an intensity of 50 mJ / cm ² was irradiated. After the exposure, the photoresist and the colored film of the polyimide precursor were developed at the same time by immersing in a developing solution composed of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. Further, the polyimide precursor colored film thus obtained was heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere to obtain a polyimide red pattern film having a film thickness of 1.0 μm.

Thereafter, in the same manner, patterns of green paste and blue paste were formed to obtain a color filter having three primary colors of red, green and blue.

The resulting color filter was spin-coated with an acrylic resin solution and heated at 100 ° C. for 5 minutes and at 260 ° C. for 30 minutes to form a color filter transparent protective film having a thickness of 1.0 μm. Obtained. No transparent conductive film was formed on the transparent protective film. (Alignment Treatment / Creation of Liquid Crystal Display Device) An alignment film (6, 13) was printed on the outermost surface of the color filter substrate and the liquid crystal display device substrate for active drive, dried and baked.

In this embodiment, the resin component of the alignment film is 2,
A polyimide containing 2-bis [4- (p-aminophenoquinone) phenylpropane] and pyromellitic dianhydride as main components was adopted.

The resistance value of the alignment film was changed by changing the kind and concentration of indium tin oxide of the metal particles in the polyimide as needed. The particle size of the indium tin oxide added to the alignment film was selected to be 5 to 20 nm. The added metal particles were surface-treated as required. Each alignment film was printed on a substrate for a liquid crystal display device, and then a rubbing treatment for aligning the liquid crystal was applied to the alignment film.

As the liquid crystal (7), commercially available fluorine nematic liquid crystal or the like was used.

The rubbing directions on the upper and lower interfaces were substantially parallel to each other, and the angle with the direction of the applied electric field was 75 °.
Dielectric anisotropy Δε is positive between these substrates and its value is 7.
The nematic liquid crystal composition of No. 1 was sandwiched.

Cell gap has spherical polymer beads (8)
Dispersed between the substrates and sandwiched between them, 4.0 μm
And Two polarizing plates [G1220DU manufactured by Nitto Denko Corporation]
In (1), the panel was sandwiched, the polarization transmission axis of one of the polarizing plates was set in the rubbing direction, and the other was set at a right angle, that is, an angle of 15 ° with the direction of the applied electric field. In this embodiment, a normally black characteristic is adopted in which a dark state is obtained at a low voltage (voltage off) and a bright state is obtained at a high voltage (voltage on).

The volume resistance of the liquid crystal is 7.00 × 10 ¹⁴ Ω · c.
It was m. Thus, the active drive type liquid crystal display device as shown in FIG. 1 was obtained. [Sensory evaluation of image sticking] A sensory evaluation of image sticking was performed using the obtained liquid crystal display device. Ten liquid crystal display devices of each level were prepared, and ten observers alternately observed the display and scored. No seizure was scored as 1 point, and as the degree of seizure became worse, the score was increased, and severe seizure was scored as 5 points. The average score of 10 observers was used as the score representing each level of burn-in. The average score of 3 or more is the seizure of OK level as a product. That is, if the display quality burn-in level is between 1 and 3 points, the product is an OK level. After the black and white checkered flag was continuously displayed on the screen for 1 hour, the image sticking was changed to halftone display and the image sticking was scored by the above method.

The scored results are shown in Table 1. Here, for example, 1.50E + 15 means 1.50 × 10 ¹⁵ Ω · c.
It means m. When the volume resistance value of the liquid crystal is Rlc, the volume resistance value of the alignment film on the substrate having the active element and the pixel electrode is Ral1, and the volume resistance value of the alignment film on the opposing substrate is Ral2, 0.98 In the level 2 to the level 10 where xRlc ≧ Ral1 ≧ Ral2 was satisfied, the image sticking was OK. Among them, Level 3 to Level 10 had good display quality.

[0118]

[Table 1]

Example 2 Similar to Example 1, an IPS type liquid crystal display device was produced. However, the liquid crystal used was a mixed liquid crystal containing a cyano liquid crystal. When the resistance value of the liquid crystal was measured, it was 5.00 ×
It was 10 ¹³ Ω · cm. The results of scoring are shown in Table 2.
The seizure was OK level 13 to 21 satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2. Above all, the display quality of Level 14 to Level 21 was good.

[0120]

[Table 2]

Example 3 Similar to Examples 1 and 2, an IPS type liquid crystal display device was produced. Indium oxide, tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide, zinc oxide, and mixtures thereof were dispersed in the alignment film as metal particles, and the respective resistance values correspond to the resistance values shown in Tables 1 and 2. Was prepared as follows. The particle size of the metal particles added to the alignment film is 5 to 2
The one with 0 nm was selected. The metal particles were surface-treated as needed. The results of the sensory evaluation of burn-in at each resistance value agree with the results of Table 1 and Table 2, and 0.98 × Rlc ≧
The display quality was OK level when Ral1 ≧ Ral2 was satisfied.

Example 4 Similar to Examples 1 and 2, an IPS type liquid crystal display device was produced. However, an alignment film material containing a metal alkoxide was used. As the metal alkoxide, In (OC
H (CH ₃ ) ₂ ) ₃ , Sn (OCH (CH ₃ ) ₂ ) ₄ , Zn
(OCH (CH ₃ ) ₂ ) ₂ , Cd (OCH (CH ₃ ) ₂ ) ₂ ,
In (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₃ , Sn (OCH ₂ CH
_{2 CH 2 CH 3) 4,} Zn (OCH 2 CH 2 CH 2 CH 3) 2,
Cd (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₂ , In (OC
₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn (OC ₂ H ₅ ) ₂ , C
Those having d (OC ₂ H ₅ ) ₂ in the resin composition of the alignment film were used, and the resistance values were respectively adjusted so as to match the resistance values in Tables 1 and 2. The results of the sensory evaluation of burn-in at each resistance value agree with the results of Tables 1 and 2, and are 0.98 × R.
The display quality was an OK level at a level satisfying lc ≧ Ral1 ≧ Ral2.

Example 5 In the production of the color filters of Examples 1 to 4, after forming a transparent protective film, a columnar article (14) having a height of 4 μm and an area of 100 μm was formed on the substrate using a photosensitive acrylic resin. The spacers were formed periodically to serve as spacers for maintaining the cell gap.
Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination. The IPS as shown in FIG. 2 as in the first to fourth embodiments.
A liquid crystal display device of the type was prepared, and a burn-in sensory evaluation was performed. The burn-in sensory evaluation at each resistance value was in agreement with the results of Table 1 and Table 2, and the display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 6 A liquid crystal display device of the twisted nematic (TN) system was used. [Production of Liquid Crystal Display Device] Two transparent glass substrates (2) having a thickness of 0.7 mm are used as substrates. (Preparation of substrate having active element and pixel electrode)
A thin film transistor, a pixel electrode (5) and the like were formed on one of the two glass substrates to obtain a liquid crystal display device substrate for active driving. The structure of this TFT array is TN
It has a system structure, and by using the common electrode on the color filter side, a voltage can be applied vertically to the glass substrate. (Production of Color Filter Substrate) The color filter substrate was produced in the same manner as in Example 1. However, after forming the transparent protective film (11), an ITO film (15) is formed as a transparent conductive film by a sputtering method.
Was formed. The ITO film on the color filter serves as a common electrode. (Alignment Treatment / Creation of Liquid Crystal Display Device) An alignment film (6, 13) was printed on the outermost surface of the color filter substrate and the liquid crystal display device substrate for active drive, dried and baked.

In this embodiment, a polyimide type alignment film is used as the resin component of the alignment film.

The resistance value of the alignment film was changed by changing the kind and concentration of indium tin oxide of the metal particles in the alignment film as needed. The grain size of indium tin oxide added to the alignment film is 5 to
20 nm was selected. The metal particles were surface-treated as needed. Each alignment film was printed on a substrate for a liquid crystal display device, and then a rubbing treatment for aligning the liquid crystal was applied to the alignment film.

As the liquid crystal (7), a commercially available nematic liquid crystal or the like was used.

The rubbing directions on the upper and lower interfaces are substantially perpendicular to each other, and the angle with the direction of the applied electric field is parallel. A nematic liquid crystal composition having a positive dielectric anisotropy Δε was sandwiched between these substrates.

Cell gap is spherical polymer beads (8)
4.5 μm with the liquid crystal enclosed in a liquid crystal
And Two polarizing plates (1) [G1220 manufactured by Nitto Denko Corporation]
DU] to sandwich the panel, and set the polarization transmission axis of one of the polarizing plates in the rubbing direction and the other at right angles. In this embodiment, a normally white characteristic is adopted in which a bright state is obtained at a low voltage (voltage off) and a dark state is obtained at a high voltage (voltage on).

The volume resistance of the liquid crystal is 3.42 × 10 ¹⁴ Ω · c.
It was m. Thus, an active drive type liquid crystal display device was obtained. [Sensory evaluation of image sticking] The sensory evaluation of image sticking was performed in the same manner as in Example 1.

The scored results are shown in Table 3. 0.98 x R
The seizure was OK level in the levels 23 to 31 satisfying lc ≧ Ral1 ≧ Ral2. Above all, the display quality of Level 24 to Level 31 was good.

[0132]

[Table 3]

Example 7 A TN type liquid crystal display device was produced in the same manner as in Example 6.
However, the liquid crystal used was changed. The alignment film was also changed.
When the resistance value of the liquid crystal was measured, it was 5.12 × 10 ¹³ Ω.
It was cm. The scored results are shown in Table 4. 0.98 x
The seizure was OK in the levels 34 to 42 satisfying Rlc ≧ Ral1 ≧ Ral2. Above all, level 35-
Level 42 had a good display quality.

[0134]

[Table 4]

Example 8 A TN type liquid crystal display device was produced in the same manner as in Examples 6 and 7. Indium oxide, tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide, zinc oxide, and a mixture thereof were dispersed in the alignment film as metal particles, and the resistance values thereof correspond to the resistance values of Tables 3 and 4, respectively. Was prepared as follows. The particle size of the metal particles added to the alignment film is 5 to 2
The one with 0 nm was selected. The metal particles were surface-treated as needed. The results of the sensory evaluation of burn-in at each resistance value agree with the results of Table 3 and Table 4, and 0.98 × Rlc ≧
The display quality was OK level when Ral1 ≧ Ral2 was satisfied.

Example 9 A TN type liquid crystal display device was manufactured in the same manner as in Examples 6 and 7.
It was However, if the alignment film material contains a metal alkoxide,
Was used. As the metal alkoxide, In (OCH
(CH₃)₂)₃, Sn (OCH (CH₃)₂)_Four, Zn (O
CH (CH₃)₂)₂, Cd (OCH (CH₃)₂)₂, In
(OCH₂CH₂CH₂CH₃)₃, Sn (OCH₂CH₂C
H₂CH₃)_Four, Zn (OCH₂CH₂CH₂CH₃)₂, Cd
(OCH ₂CH₂CH₂CH₃)₂, In (OC₂H_Five)₃, S
n (OC₂H_Five)_Four, Zn (OC₂H _Five)₂, Cd (OC
₂H_Five)₂Each having a resin composition in the alignment film
The resistance values match those in Table 3 and Table 4, respectively.
I prepared it like this. Burn-in sensory evaluation at each resistance value
The results are in agreement with those of Tables 3 and 4, and 0.98 × Rlc ≧ R
The display quality is OK level when al1 ≧ Ral2 is satisfied.
It was

Example 10 In the production of the color filters of Examples 6 to 9, after forming a transparent protective film and a transparent conductive film, a columnar article having a height of 4 μm and an area of 100 μm was formed on the substrate using a photosensitive acrylic resin. (14) was periodically formed to serve as a spacer for maintaining the cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination. A liquid crystal display device of the TN system was prepared in the same manner as in Examples 6 to 9 and a burn-in sensory evaluation was performed. The burn-in sensory evaluation at each resistance value was in agreement with the results of Tables 3 and 4, and the display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 11 This was carried out in a vertical alignment type liquid crystal display device. [Production of Liquid Crystal Display Device] Two transparent glass substrates (1) having a thickness of 0.7 mm are used as substrates. (Preparation of substrate having active element and pixel electrode)
A thin film transistor, a pixel electrode (5) and the like were formed on one of the two glass substrates to obtain a liquid crystal display device substrate for active driving. The structure is an electrode of a vertical alignment type structure. The pixel electrode has a zigzag shape.
A voltage can be applied almost perpendicularly to the glass substrate between the common electrode (15) on the color filter side. The shape of the zigzag electrodes and the projections for divided alignment can control the direction of directors of liquid crystal molecules when a voltage is applied to the liquid crystal display device. (Production of Color Filter Substrate) After forming a black matrix using a chromium-based metal, pixels were formed in the same manner as in Example 1. After forming pixels, ITO was formed as a transparent conductive film (15). Next, the protrusions (16) for split orientation were formed using a photosensitive resin. (Alignment Treatment / Preparation of Liquid Crystal Display Device) An alignment film was printed on the outermost surface of the color filter substrate with projections for divided alignment and the substrate for liquid crystal display device for active driving, dried and baked.

In this embodiment, a polyimide vertical alignment film is used as the resin component of the alignment film.

The resistance value of the alignment film was changed by changing the kind and concentration of indium tin oxide of the metal particles in the alignment film as needed. The grain size of indium tin oxide added to the alignment film is 5 to
20 nm was selected. The metal particles were surface-treated as needed. Each alignment film was printed on a substrate for a liquid crystal display device. No rubbing treatment was applied.

As the liquid crystal (7), a commercially available nematic liquid crystal having negative dielectric anisotropy or the like was used.

The liquid crystal is aligned almost vertically along the surface shape of the substrate. The portion on which the protrusion for alignment division is formed is oriented almost vertically along the shape of the protrusion.

Cell gap is spherical polymer beads (8)
4.5 μm with the liquid crystal enclosed in a liquid crystal
And Two polarizing plates [G1220DU manufactured by Nitto Denko Corporation]
The panel was sandwiched between, and the angle formed by one polarizing plate and the other was orthogonal. In this embodiment, a normally black characteristic is adopted in which a dark state is obtained at a low voltage (voltage off) and a bright state is obtained at a high voltage (voltage on).

The volume resistance of liquid crystal is 7.63 × 10 ¹³ Ω · c.
It was m. In this way, an active drive type liquid crystal display device as shown in FIG. 5 was obtained. [Sensory evaluation of image sticking] The sensory evaluation of image sticking was performed in the same manner as in Example 1.

Table 5 shows the scored results. 0.98 x R
The seizure was OK level in the levels 44 to 52 satisfying lc ≧ Ral1 ≧ Ral2. Above all, the display quality was good in the levels 45 to 52.

[0146]

[Table 5]

Example 12 A vertical alignment type liquid crystal display device was produced in the same manner as in Example 11. However, an additive was added to the liquid crystal used. When the resistance value of the liquid crystal was measured, it was 1.30 × 10 ¹³ Ω · cm. The scored results are shown in Table 6. 0.98 × Rlc ≧ R
The seizure was OK level in the levels 55 to 63 satisfying al1 ≧ Ral2. Above all, level 56 to level 63
The display quality was good.

[0148]

[Table 6]

Example 13 A vertical alignment type liquid crystal display device was produced in the same manner as in Examples 11 and 12. Indium oxide, tin oxide as metal particles,
Cadmium-doped tin oxide, titanium oxide, titanium dioxide,
Zinc oxide and a mixture thereof were dispersed in the alignment film, and the resistance values were adjusted so as to match the resistance values shown in Tables 5 and 6, respectively. The metal particles added to the alignment film had a particle size of 5 to 20 nm. The metal particles were surface-treated as needed. The burn-in sensory evaluation results at each resistance value agree with the results of Tables 5 and 6, and are 0.98 ×
The display quality was OK level at the level satisfying Rlc ≧ Ral1 ≧ Ral2.

Example 14 A vertical alignment type liquid crystal display device was manufactured in the same manner as in Examples 11 and 12. However, an alignment film material containing a metal alkoxide was used. As the metal alkoxide, In
(OCH (CH ₃ ) ₂ ) ₃ , Sn (OCH (CH ₃ ) ₂ ) ₄ ,
_{Zn (OCH (CH 3) 2} ) 2, Cd (OCH (C
_{H 3) 2) 2, In} (OCH 2 CH 2 CH 2 CH 3) 3, Sn
(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , Zn (OCH ₂ CH ₂ C
_{H 2 CH 3) 2, Cd} (OCH 2 CH 2 CH 2 CH 3) 2, In
(OC ₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn (OC ₂ H ₅ )
₂ and Cd (OC ₂ H ₅ ) ₂ were respectively used in the resin composition of the alignment film, and the resistance values were respectively adjusted so as to match the resistance values shown in Tables 1 and 2. The burn-in sensory evaluation results at the respective resistance values agree with the results of Table 5 and Table 6, and are 0.98.
× Rlc ≧ Ral1 ≧ Ral2, and the display quality was OK.

Example 15 In the production of the color filters of Examples 11-14,
After forming the alignment division projections, a columnar material having a height of 4 μm and an area of 100 μm was periodically formed on the substrate using a photosensitive resin to form a spacer for maintaining a cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination.
A vertical alignment type liquid crystal display device was prepared in the same manner as in Examples 11 to 14, and a burn-in sensory evaluation was performed. The burn-in sensory evaluations at the respective resistance values agree with the results of Tables 5 and 6,
The display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 16 This was carried out in a (vertical alignment) type liquid crystal display device. [Production of Liquid Crystal Display Device] Two transparent glass substrates (2) having a thickness of 0.7 mm and having a polished surface are used as substrates. (Preparation of substrate having active element and pixel electrode)
A substrate for a liquid crystal display device for active driving was produced in the same manner as in Example 11. (Production of Color Filter Substrate) Unlike Example 11, the black matrix was not formed using the light shielding film. The black matrix was prepared by stacking (17) two colors of the colored layers forming the blue, red and green pixels. After forming pixels and a black matrix, ITO was formed as a transparent conductive film (15). Next, a protrusion for split orientation was formed using a photosensitive resin. (Alignment Treatment / Preparation of Liquid Crystal Display Device) An alignment film was printed on the outermost surface of the color filter substrate with projections for divided alignment and the substrate for liquid crystal display device for active driving, dried and baked.

In this embodiment, a polyimide vertical alignment film is used as the resin component of the alignment film.

If necessary, the resistance value of the alignment film was changed by changing the kind and concentration of indium tin oxide of the metal particles in the alignment film. The grain size of indium tin oxide added to the alignment film is 5 to
20 nm was selected. The metal particles were surface-treated as needed. Each alignment film was printed on a substrate for a liquid crystal display device. No rubbing treatment was applied.

As the liquid crystal (7), a commercially available nematic liquid crystal having negative dielectric anisotropy or the like was used.

The liquid crystal is aligned almost vertically along the surface shape of the substrate. The portion on which the projection for splitting the orientation is formed is oriented substantially vertically along the shape of the projection.

The cell gap was 4.5 μm when spherical polymer beads were dispersed and sandwiched between the substrates and the liquid crystal was sealed. The panel was sandwiched between two polarizing plates [G1220DU manufactured by Nitto Denko Corporation], and the angle formed by one polarizing plate and the other was orthogonal. In this embodiment, a normally black characteristic is adopted in which a dark state is obtained at a low voltage (voltage off) and a bright state is obtained at a high voltage (voltage on).

The volume resistance of the liquid crystal is 5.42 × 10 ¹⁴ Ω · c.
It was m. Thus, an active drive type liquid crystal display device as shown in FIG. 7 was obtained. [Sensory evaluation of image sticking] The sensory evaluation of image sticking was performed in the same manner as in Example 1.

The scored results are shown in Table 7. 0.98 x R
The seizure was OK level in the levels 65 to 73 satisfying lc ≧ Ral1 ≧ Ral2. Above all, the display quality was good in the levels 66 to 73.

[0160]

[Table 7]

Example 17 A vertical alignment type liquid crystal display device was produced in the same manner as in Example 16. However, the composition of the liquid crystal used was changed. When the resistance value of the liquid crystal was measured, it was 3.40 × 10 ¹³ Ω · cm. The scored results are shown in Table 8. 0.98 × Rlc ≧
The seizure was OK in the level 76 to the level 84 satisfying Ral1 ≧ Ral2. Above all, level 77 to level 8
No. 4 had a good display quality.

[0162]

[Table 8]

Example 18 A vertical alignment type liquid crystal display device was manufactured in the same manner as in Examples 16 and 17. Indium oxide, tin oxide as metal particles,
Cadmium-doped tin oxide, titanium oxide, titanium dioxide,
Zinc oxide and a mixture thereof were dispersed in the alignment film, and the resistance values were adjusted so as to match the resistance values shown in Tables 7 and 8. The metal particles added to the alignment film had a particle size of 5 to 20 nm. The metal particles were surface-treated as needed. The burn-in sensory evaluation results at the respective resistance values agree with the results of Tables 7 and 8 and are 0.98 ×
The display quality was OK level at the level satisfying Rlc ≧ Ral1 ≧ Ral2.

Example 19 A vertical alignment type liquid crystal display device was produced in the same manner as in Examples 16 and 17. However, an alignment film material containing a metal alkoxide was used. As the metal alkoxide, In
(OCH (CH ₃ ) ₂ ) ₃ , Sn (OCH (CH ₃ ) ₂ ) ₄ ,
_{Zn (OCH (CH 3) 2} ) 2, Cd (OCH (C
_{H 3) 2) 2, In} (OCH 2 CH 2 CH 2 CH 3) 3, Sn
(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , Zn (OCH ₂ CH ₂ C
_{H 2 CH 3) 2, Cd} (OCH 2 CH 2 CH 2 CH 3) 2, In
(OC ₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn (OC ₂ H ₅ )
₂ and Cd (OC ₂ H ₅ ) ₂ were used in the resin composition of the alignment film, and the resistance values were adjusted so as to match the resistance values shown in Tables 7 and 8. The burn-in sensory evaluation results at the respective resistance values agree with the results of Tables 7 and 8, and are 0.98.
× Rlc ≧ Ral1 ≧ Ral2, and the display quality was OK.

Example 20 In the production of the color filters of Examples 16 to 19,
In addition to the place where two layers of pixels were laminated to form a black matrix, a place where the three colors of the colored layers constituting the pixels were overlapped was provided. Alignment division projections (20) on columnar bodies and openings on which three colored layers on the substrate are stacked using a photosensitive resin
Was formed. The spacers for maintaining the cell gap were formed by forming the columnar bodies at the locations where the three colored layers and the photosensitive resin were formed. The columnar body has a height of 4 μm and an area of 100 μm.
m columnar objects (19) were formed to be periodic.

An alignment film is printed on the outermost surface of the color filter substrate and the substrate on which the active element is formed, dried,
Baked. Spherical polymer beads were not used during lamination. Similarly to Examples 16 to 19, a vertical alignment type liquid crystal display device as shown in FIG. 8 was prepared and a burn-in sensory evaluation was performed. The burn-in sensory evaluations at the respective resistance values agree with the results of Table 7 and Table 8, and 0.98 × Rlc ≧ Ral1
The display quality was OK level when ≧ Ral2 was satisfied.

Example 21 Reflective low-temperature polysilicon T having an SRAM incorporated in a pixel
An FT-Twisted Nematic (TN) liquid crystal display device was used. [Production of Liquid Crystal Display Device] Two transparent glass substrates having a thickness of 0.5 mm are used as substrates. (Preparation of substrate having active element and pixel electrode)
A thin film transistor, an SRAM, a specular reflection pixel electrode and the like were formed on one of the two glass substrates to prepare a substrate for a liquid crystal display device for active driving. The structure of this TFT array is a TN type structure, and a voltage can be applied vertically to the glass substrate by using the common electrode on the color filter side. (Production of Color Filter Substrate) The color filter substrate was produced in the same manner as in Example 1. However, after forming the transparent protective film, an ITO film was formed as a transparent conductive film by a sputtering method. The ITO film on the color filter serves as a common electrode. (Alignment Treatment / Production of Liquid Crystal Display Device) An alignment film was printed on the outermost surface of the color filter substrate and the substrate for the liquid crystal display device for active driving, dried and baked.

In this embodiment, a polyimide type alignment film is used as the resin component of the alignment film.

The resistance value of the alignment film was changed by changing the kind and concentration of indium tin oxide of the metal particles in the alignment film as needed. The grain size of indium tin oxide added to the alignment film is 5 to
20 nm was selected. The metal particles were surface-treated as needed. Each alignment film was printed on a substrate for a liquid crystal display device, and then a rubbing treatment for aligning the liquid crystal was applied to the alignment film.

As the liquid crystal, a commercially available nematic liquid crystal or the like was used.

The rubbing directions on the upper and lower interfaces are substantially perpendicular to each other, and the angle with the direction of the applied electric field is parallel. A nematic liquid crystal composition having a positive dielectric anisotropy Δε was sandwiched between these substrates.

The cell gap was set to 3.5 μm in a state where liquid crystal was sealed by holding spherical polymer beads dispersed between substrates. The panel was sandwiched between two polarizing plates [G1220DU manufactured by Nitto Denko Corporation], the polarization transmission axis of one polarizing plate was set in the rubbing direction, and the other was orthogonal thereto. In this embodiment, a normally white characteristic is adopted in which a bright state is obtained at a low voltage (voltage off) and a dark state is obtained at a high voltage (voltage on).

The volume resistance of liquid crystal is 3.12 × 10 ¹⁴ Ω · c.
It was m. Thus, an active drive type liquid crystal display device was obtained. [Sensory evaluation of image sticking] The sensory evaluation of image sticking was performed in the same manner as in Example 1.

Table 9 shows the scored results. 0.98 x R
The seizure was OK level in the levels 86 to 94 satisfying lc ≧ Ral1 ≧ Ral2. Above all, the display quality was good in the levels 87 to 94.

[0175]

[Table 9]

Embodiment 22 Similar to Embodiment 21, a reflection type low temperature polysilicon TFT having a built-in SRAM in a pixel-twisted nematic (T).
This was carried out in the N) type liquid crystal display device. However, the liquid crystal used was changed. The alignment film was also changed. When the resistance value of the liquid crystal was measured, it was 4.13 × 10 ¹¹ Ω · cm. The scored results are shown in Table 10. 0.98 × Rlc ≧
The seizure was OK level from level 97 to level 105 satisfying Ral1 ≧ Ral2. Above all, the display quality was good in the levels 96 to 105.

[0177]

[Table 10]

Embodiment 23 Similar to Embodiments 21 and 22, the present invention was carried out in a reflective low temperature polysilicon TFT-twisted nematic (TN) type liquid crystal display device in which an SRAM was incorporated in a pixel. However, indium oxide, tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide, zinc oxide, and a mixture thereof were dispersed in the alignment film as metal particles, and the resistance values were changed to the resistance values shown in Tables 9 and 10. Formulated to match. The particle size of the metal particles added to the alignment film is 5 to
20 nm was selected. The metal particles were surface-treated as needed. The results of the sensory evaluation of image sticking at the respective resistance values agree with the results of Tables 9 and 10, and are 0.98 × R.
The display quality was an OK level at a level satisfying lc ≧ Ral1 ≧ Ral2.

Example 24 A TN type liquid crystal display device was produced in the same manner as in Examples 21 and 22. However, an alignment film material containing a metal alkoxide was used. As the metal alkoxide, In
(OCH (CH ₃ ) ₂ ) ₃ , Sn (OCH (CH ₃ ) ₂ ) ₄ ,
_{Zn (OCH (CH 3) 2} ) 2, Cd (OCH (C
_{H 3) 2) 2, In} (OCH 2 CH 2 CH 2 CH 3) 3, Sn
(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , Zn (OCH ₂ CH ₂ C
_{H 2 CH 3) 2, Cd} (OCH 2 CH 2 CH 2 CH 3) 2, In
(OC ₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn (OC ₂ H ₅ )
₂ and Cd (OC ₂ H ₅ ) ₂ were used in the resin composition of the alignment film, and the resistance values were respectively adjusted so as to match the resistance values shown in Tables 9 and 10. The burn-in sensory evaluation results at the respective resistance values agree with the results of Tables 9 and 10, and are 0.9
Display quality is OK at a level satisfying 8 × Rlc ≧ Ral1 ≧ Ral2
It was a level.

Example 25 In the production of the color filters of Examples 21 to 24,
After forming the transparent protective film and the transparent conductive film, a photosensitive acrylic resin is used to form a height of 4 μm on the substrate and an area of 100 μm.
Columnar objects of m were periodically formed to serve as spacers for maintaining the cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination. Liquid crystal display devices were prepared in the same manner as in Examples 21 to 24, and a burn-in sensory evaluation was performed. The burn-in sensory evaluation at each resistance value was in agreement with the results of Table 9 and Table 10, and the display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 26 An in-plane switching (IPS) liquid crystal display device was used. [Fabrication of Liquid Crystal Display Device] A liquid crystal display device was fabricated in the same manner as in Example 1. However, the frame and the black matrix used a resin in which titanium oxynitride was dispersed. The production was performed as follows.

Using a homogenizer, 10 g of titanium oxynitride, 57 g of N-methyl-2-pyrrolidone and 13 g of butyl cellosolve were used together with 100 g of glass beads at 7,000 r.
After dispersion treatment for 30 minutes at pm, the glass beads were removed by filtration to obtain a dispersion liquid having a pigment concentration of 12.5% by weight.

40 g of the dispersion was added to the above-mentioned polymer concentration 1
15 g of 0 wt% polyimide precursor solution was added and mixed,
A black paste was prepared. After applying this paste on glass, it was semi-cured at 125 ° C. for 20 minutes. After that, a positive resist was applied with a spinner and dried at 80 ° C. for 20 minutes. The photoresist was exposed using a photomask, and the substrate was dipped in an alkali developing solution to simultaneously develop the positive resist and etch the polyimide precursor.
Then, the positive photoresist was peeled off with methyl cellosolve acetate and further cured at 280 ° C. for 30 minutes. [Sensing evaluation by burn-in] Sensory evaluation was performed in the same manner as in Example 1.

Table 11 shows the results of scoring. 0.98 x
The seizure was OK level from level 2 to level 10 satisfying Rlc ≧ Ral1 ≧ Ral2. Among them, Level 3 to Level 10 had good display quality.

[0185]

[Table 11]

Example 27 An IPS liquid crystal display device was produced in the same manner as in Example 26. However, the liquid crystal used was a mixed liquid crystal containing a cyano liquid crystal. When the resistance value of the liquid crystal was measured, it was 5.00 ×
It was 10 ¹³ Ω · cm. The scored results are shown in Table 12. Level 13 that satisfies 0.98 × Rlc ≧ Ral1 ≧ Ral2
The seizure was OK level 21. Above all, the display quality of Level 14 to Level 21 was good.

[0187]

[Table 12]

Example 28 An IPS type liquid crystal display device was produced in the same manner as in Examples 27 and 28. Indium oxide, tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide, zinc oxide, and a mixture thereof were dispersed in the alignment film as metal particles, and the respective resistance values correspond to the resistance values in Tables 11 and 12. Was prepared as follows. The metal particles added to the alignment film had a particle size of 5 to 20 nm. The metal particles were surface-treated as needed. The results of the burn-in sensory evaluations at the respective resistance values agree with the results of Examples 26 and 27 of Table 11 and Table 12, and the display quality is OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2. It was

Example 29 An IPS type liquid crystal display device was produced in the same manner as in Examples 27 and 28. However, an alignment film material containing a metal alkoxide was used. As the metal alkoxide, In
(OCH (CH ₃ ) ₂ ) ₃ , Sn (OCH (CH ₃ ) ₂ ) ₄ ,
_{Zn (OCH (CH 3) 2} ) 2, Cd (OCH (C
_{H 3) 2) 2, In} (OCH 2 CH 2 CH 2 CH 3) 3, Sn
(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , Zn (OCH ₂ CH ₂ C
_{H 2 CH 3) 2, Cd} (OCH 2 CH 2 CH 2 CH 3) 2, In
(OC ₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn (OC ₂ H ₅ )
₂ and Cd (OC ₂ H ₅ ) ₂ were used in the resin composition of the alignment film, and the resistance values were adjusted so as to match the resistance values in Tables 11 and 12. The results of the organoleptic evaluation at each resistance value agree with the results of Examples 26 and 27 in Table 11 and Table 12, and 0.98 × Rlc ≧ Ral1 ≧ Ra.
The display quality was an OK level at a level satisfying l2.

Example 30 In the production of the color filters of Examples 26 to 29,
After forming the transparent protective film, a columnar article (14) having a height of 4 μm and an area of 100 μm is formed on the substrate by using a photosensitive acrylic resin.
Were periodically formed to serve as spacers for maintaining the cell gap. Then print an alignment film on the outermost surface and dry it.
Baked. Spherical polymer beads were not used during lamination. As in Examples 1 to 4, I as shown in FIG.
A PS type liquid crystal display device was prepared and a burn-in sensory evaluation was performed. Table 1 shows the burn-in sensory evaluation at each resistance value.
1, in accordance with the results of Example 26, Example 27 in Table 12,
The display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 31 The same operation as in Example 1 was carried out in a twisted nematic (TN) type liquid crystal display device. However, a resin in which titanium oxynitride was dispersed was used for forming the frame and the black matrix. Similar to Example 6, a liquid crystal display device was produced at a level in which the alignment film was changed, and sensory evaluation was performed. The sensory evaluation of image sticking was performed in the same manner as in Example 1. The scored results are shown in Table 13. Although the image sticking was OK in the levels 23 to 31 satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2, the peripheral portion of the screen tended to be slightly burned in compared with the central portion. Levels 24 to 31 were particularly good in display quality.

[0192]

[Table 13]

Example 32 A TN type liquid crystal display device was produced in the same manner as in Example 31. However, the liquid crystal used was changed. The alignment film was also changed. The scored results are shown in Table 14. 0.98 × Rlc ≧ R
The seizure was OK at the level 34 to the level 42 satisfying al1 ≧ Ral2, but the peripheral portion of the screen tended to be seized compared to the central portion. Level 35 to level 42 were good in display quality.

[0194]

[Table 14]

Example 33 A TN type liquid crystal display device was produced in the same manner as in Examples 31 and 32. Indium oxide, tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide, zinc oxide, and a mixture thereof were dispersed in the alignment film as metal particles, and the resistance values thereof corresponded to those of Tables 31 and 14, respectively. Was prepared as follows. The metal particles added to the alignment film had a particle size of 5 to 20 nm. The metal particles were surface-treated as needed. The results of the burn-in sensory evaluation at the respective resistance values are shown in Tables 13 and 14 as Example 31 and Example 3.
In accordance with the result of No. 2, the display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 34 Similar to Examples 31 and 32, a TN type liquid crystal display device was manufactured.
Made However, the alignment film material does not contain metal alkoxide.
I used Mumu. As the metal alkoxide, In (O
CH (CH₃)₂)₃, Sn (OCH (CH₃)₂)_Four, Zn
(OCH (CH ₃)₂)₂, Cd (OCH (CH₃)₂)₂,
In (OCH₂CH₂CH₂CH₃)₃, Sn (OCH₂CH
₂CH₂CH₃)_Four, Zn (OCH₂CH₂CH₂CH₃)₂,
Cd (OCH₂CH₂CH₂CH₃)₂, In (OC
₂H_Five)₃, Sn (OC₂H_Five)_Four, Zn (OC₂H_Five)₂, C
d (OC₂H_Five)₂Each in the resin composition of the alignment film
The resistance values of Table 3 and Table 4 respectively.
It was prepared to do. Burn-in officer at each resistance value
The performance evaluation results are shown in Tables 13 and 14 as Examples 31 and 32.
And 0.98 × Rlc ≧ Ral1 ≧ Ral2 is satisfied.
The display quality was OK level.

Example 35 In the production of the color filters of Examples 31 to 34,
After forming the transparent protective film and the transparent conductive film, a photosensitive acrylic resin is used to form a height of 4 μm and an area of 100 μm on the substrate.
The columnar bodies (14) were periodically formed to serve as spacers for maintaining the cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination. T as in Examples 6-9
An N-type liquid crystal display device was prepared and a burn-in sensory evaluation was performed. Table 1 shows the burn-in sensory evaluation at each resistance value.
3, in agreement with the result of Table 14, 0.98 × Rlc ≧ Ral1 ≧
The display quality was OK level when Ral2 was satisfied.

Example 36 This was carried out in a vertical alignment type liquid crystal display device. [Production of Liquid Crystal Display Device] A liquid crystal display device was produced in the same manner as in Example 11. However, in the production of the color filter substrate, the black matrix was formed using the resin containing titanium oxynitride. Example 11 is also applied to the alignment treatment / liquid crystal display device.
The same operation as described above was performed to obtain an active drive type liquid crystal display device as shown in FIG. [Sensory evaluation of image sticking] The sensory evaluation of image sticking was performed in the same manner as in Example 1.

Table 15 shows the scored results. 0.98 x
The image sticking was OK at the level 44 to the level 52 satisfying Rlc ≧ Ral1 ≧ Ral2, but there was a tendency for the image sticking in the peripheral portion of the screen as compared with the central portion. Above all, level 4
The display quality of 5 to 52 was good.

[0200]

[Table 15]

Example 37 A vertical alignment type liquid crystal display device was produced in the same manner as in Example 36. However, the resistance value of the liquid crystal was adjusted by adding the additive to the liquid crystal to be used as in Example 12. The scored results are shown in Table 16. The seizure was OK level in the levels 55 to 63 satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2. Above all, the display quality was good in the levels 56 to 63.

[0202]

[Table 16]

Example 38 A vertical alignment type liquid crystal display device was produced in the same manner as in Examples 36 and 37. Indium oxide, tin oxide as metal particles,
Cadmium-doped tin oxide, titanium oxide, titanium dioxide,
Zinc oxide and a mixture thereof were dispersed in the alignment film, and the resistance values were adjusted so as to match the resistance values shown in Tables 15 and 16. The metal particles added to the alignment film had a particle size of 5 to 20 nm. The metal particles were surface-treated as needed. The burn-in sensory evaluation results at the respective resistance values agree with the results of Tables 15 and 16,
The display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 39 A vertical alignment type liquid crystal display device was produced in the same manner as in Examples 36 and 37. However, as in Example 14, an alignment film material containing a metal alkoxide was used. Examples of the metal alkoxide include In (OCH (CH ₃ ) ₂ ) ₃ and Sn (O
CH (CH ₃ ) ₂ ) ₄ , Zn (OCH (CH ₃ ) ₂ ) ₂ , Cd
(OCH (CH ₃ ) ₂ ) ₂ , In (OCH ₂ CH ₂ CH ₂ CH
₃ ) ₃ , Sn (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , Zn (OC
H ₂ CH ₂ CH ₂ CH ₃ ) ₂ , Cd (OCH ₂ CH ₂ CH ₂ CH
₃ ) ₂ , In (OC ₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn
A resin having (OC ₂ H ₅ ) ₂ and Cd (OC ₂ H ₅ ) ₂ in the resin composition of the alignment film was used, and the resistance values are shown in Table 11.
Formulation was performed so as to match the resistance values in Table 12. The results of the organoleptic evaluation at the respective resistance values agree with the results of Example 36 and Example 37 in Tables 15 and 16, and 0.98 ×
The display quality was OK level at the level satisfying Rlc ≧ Ral1 ≧ Ral2.

Example 30 In the production of the color filters of Examples 36 to 39,
After forming the alignment division projections, a columnar material having a height of 4 μm and an area of 100 μm was periodically formed on the substrate using a photosensitive resin to form a spacer for maintaining a cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination.
A vertical alignment type liquid crystal display device was prepared in the same manner as in Examples 36 to 39, and a burn-in sensory evaluation was performed. The burn-in sensory evaluation at each resistance value was in agreement with the results of Tables 15 and 16, and the display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 31 A driving circuit was formed in a reflective low temperature polysilicon TFT-twisted nematic (TN) liquid crystal display device formed on a glass substrate.

A liquid crystal display device was manufactured in the same manner as in Example 21. The color filter substrate was manufactured in the same manner as in Example 26, but after forming the transparent protective film, the ITO film was formed as the transparent conductive film by the sputtering method. The ITO film on the color filter serves as a common electrode.

In the same manner as in Example 21, the kind and concentration of indium tin oxide of the metal particles in the orientation film were changed as necessary,
The resistance value of the alignment film was changed. The particle size of the indium tin oxide added to the alignment film was selected to be 5 to 20 nm. The metal particles were surface-treated as needed. Each alignment film was printed on a substrate for a liquid crystal display device, and then a rubbing treatment for aligning liquid crystals was applied to the alignment film to manufacture a liquid crystal display device.

The sensory evaluation of image sticking was performed in the same manner as in Example 1.

Table 17 shows the scored results. 0.98 x
The image sticking was OK at the level 86 to the level 94 satisfying Rlc ≧ Ral1 ≧ Ral2, but there was a tendency for the image sticking in the peripheral portion of the screen compared to the central portion. Level 87 to level 94 had good display quality.

[0211]

[Table 17]

Example 32 The same operation as in Example 31 was carried out in a reflective low temperature polysilicon TFT-twisted nematic (TN) type liquid crystal display device. However, the liquid crystal used was changed. The alignment film was also changed. When the resistance value of the liquid crystal was measured, 4.
It was 13 × 10 ¹¹ Ω · cm. Table 18 shows the scored results.
Shown in. Level 9 satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2
Although the image sticking was OK in the range of 7 to 105, the peripheral portion of the screen had a tendency of image sticking as compared with the central portion. Level 96 to level 105 had good display quality.

[0213]

[Table 18]

Example 33 Similar to Examples 31 and 32, reflective low temperature polysilicon TF was used.
It was carried out in a liquid crystal display device of T-Twisted Nematic (TN) system. However, in the same manner as in Example 23, indium oxide, tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide, zinc oxide, and mixtures thereof were dispersed in the alignment film as metal particles, and the respective resistance values were set in Table 17. , 18 resistance values were prepared. The particle size of the metal particles added to the alignment film is 5 to 20 nm.
I chose one. The metal particles were surface-treated as needed. The burn-in sensory evaluation results at the respective resistance values agree with the results of Examples 31 and 32 in Tables 17 and 18,
The display quality was OK level at a level satisfying 0.98 × Rlc ≧ Ral1 ≧ Ral2.

Example 34 A TN type liquid crystal display device was produced in the same manner as in Examples 31 and 32. However, as in Example 24, an alignment film material containing a metal alkoxide was used. Examples of the metal alkoxide include In (OCH (CH ₃ ) ₂ ) ₃ and Sn (O
CH (CH ₃ ) ₂ ) ₄ , Zn (OCH (CH ₃ ) ₂ ) ₂ , Cd
(OCH (CH ₃ ) ₂ ) ₂ , In (OCH ₂ CH ₂ CH ₂ CH
₃ ) ₃ , Sn (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , Zn (OC
H ₂ CH ₂ CH ₂ CH ₃ ) ₂ , Cd (OCH ₂ CH ₂ CH ₂ CH
₃ ) ₂ , In (OC ₂ H ₅ ) ₃ , Sn (OC ₂ H ₅ ) ₄ , Zn
(OC ₂ H ₅ ) ₂ and Cd (OC ₂ H ₅ ) ₂ were used in the orientation film resin composition, and the resistance values are shown in Tables 9 and 1, respectively.
Formulated to match a resistance value of 0. The results of the burn-in sensory evaluation at the respective resistance values agree with the results of Examples 31 and 32 in Tables 17 and 18, and 0.98 × Rlc ≧ Ral1 ≧
The display quality was OK level when Ral2 was satisfied.

Example 35 In the production of the color filters of Examples 31 to 34,
After forming the transparent protective film and the transparent conductive film, a photosensitive acrylic resin is used to form a height of 4 μm on the substrate and an area of 100 μm.
Columnar objects of m were periodically formed to serve as spacers for maintaining the cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination. Liquid crystal display devices were prepared in the same manner as in Examples 31 to 34, and a burn-in sensory evaluation was performed. The burn-in sensory evaluation at each resistance value was in agreement with the results of Example 31 and Example 32 in Table 17 and Table 18, and was 0.98 × R.
The display quality was an OK level at a level satisfying lc ≧ Ral1 ≧ Ral2.

Example 36 A driving circuit was formed in a reflective low temperature polysilicon TFT-twisted nematic (TN) type liquid crystal display device formed on a glass substrate.

A liquid crystal display device was manufactured in the same manner as in Example 21. A color filter substrate was produced in the same manner as in Example 26, but no black matrix was formed. However, the frame was formed. As in Example 26, a resin in which titanium oxynitride is dispersed is used for the frame. After forming a transparent protective film, an ITO film was formed as a transparent conductive film by a sputtering method. The ITO film on the color filter serves as a common electrode.

In the same manner as in Example 21, the kind and concentration of indium tin oxide of the metal particles were changed in the orientation film as needed,
The resistance value of the alignment film was changed. The particle size of the indium tin oxide added to the alignment film was selected to be 5 to 20 nm. The metal particles were surface-treated as needed. Each alignment film was printed on a substrate for a liquid crystal display device, and then a rubbing treatment for aligning liquid crystals was applied to the alignment film to manufacture a liquid crystal display device.

The sensory evaluation of image sticking was performed in the same manner as in Example 1.

The results of scoring are shown in Table 19. 0.98 x
The image sticking was OK at the level 86 to the level 94 satisfying Rlc ≧ Ral1 ≧ Ral2, but there was a tendency for the image sticking in the peripheral portion of the screen compared to the central portion. Level 87 to level 94 had good display quality.

[0222]

[Table 19]

Example 37 In the manufacture of the color filter of Example 36, after the transparent protective film and the transparent conductive film were formed, the photosensitive acrylic resin was used to form columnar objects having a height of 4 μm and an area of 100 μm on the substrate. To form a spacer for maintaining the cell gap. Further, an alignment film was printed on the outermost surface, dried and fired. Spherical polymer beads were not used during lamination. Similarly to Example 36, a polarizing plate or the like was attached to manufacture a liquid crystal display device, and a burn-in sensory evaluation was performed.
The burn-in sensory evaluation at each resistance value was in agreement with the result of Example 36 in Table 19, and 0.98 × Rlc ≧ Ral1 ≧ Ral2.
The display quality was an OK level at a level satisfying the above conditions.

[0224]

According to the present invention, a liquid crystal display device with reduced image sticking can be provided.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a liquid crystal display device for explaining Examples 1 to 4 and 26 to 29.

FIG. 2 is a schematic sectional view showing a liquid crystal display device for explaining Examples 5 and 30.

FIG. 3 is a schematic sectional view showing a liquid crystal display device for explaining Examples 6 to 9 and 31 to 34.

FIG. 4 is a schematic sectional view showing a liquid crystal display device for explaining Examples 10 and 35.

FIG. 5 is a schematic sectional view showing a liquid crystal display device for explaining Examples 11 to 14 and 36 to 39.

FIG. 6 is a schematic sectional view showing a liquid crystal display device for explaining Examples 15 and 30.

FIG. 7 is a schematic cross-sectional view showing a liquid crystal display device for explaining Examples 16 to 19.

FIG. 8 is a schematic sectional view showing a liquid crystal display device for explaining an twentieth embodiment.

[Explanation of symbols]

1: Polarizing plate 2: Glass substrate 3: Gate electrode 4: Interlayer insulating film 5: Pixel electrode 6: Alignment film on substrate side with active element 7: Liquid crystal 8: Bead spacer 9: Colored pixel layer 10: Black matrix 11: Transparent protection Film 12: Common electrode 13: Alignment film 14 on the opposite side of the substrate with active elements 14: Columns 15: Transparent conductive film 16: Alignment division projections 17: Black matrix 18 formed by stacking two colored layers: Location 19 formed by stacking three colored layers: Alignment division projections formed simultaneously with 19 using the same photosensitive resin as the columnar body 20:19 made of photosensitive resin

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H090 HA03 HB07Y HB08Y HB18Y                       HC05 LA05 LA15                 2H091 FA02Y FA35Y FB02 FB13                       GA06 HA06 LA01                 2H092 GA14 HA04 HA11 JA24 PA02                       PA08 PA09 QA06

Claims (13)

[Claims] Claim: What is claimed is: 1. A liquid crystal display device comprising a liquid crystal display device substrate and a liquid crystal layer between the two liquid crystal display device substrates. A liquid crystal display device characterized by satisfying the relationship of 0.98 × Rlc ≧ Ral, where Rlc is the resistance value and Ral is the volume resistance value of the alignment film. 2. A liquid crystal display device substrate comprising two liquid crystal display device substrates with a liquid crystal interposed therebetween and having an alignment film on the side of the liquid crystal display device substrate in contact with the liquid crystal. In the liquid crystal display device having the active element and the pixel electrode on the side in contact with the liquid crystal, the volume resistance value of the liquid crystal is Rl.
c, the volume resistance value of the alignment film on the substrate having the active element and the pixel electrode is Ral1, and the volume resistance value of the alignment film on the opposing substrate is Ral2, 0.98 × Rlc ≧ Ral1, and A liquid crystal display device characterized by satisfying the relationship of 0.98 × Rlc ≧ Ral2. 3. A liquid crystal display device according to claim 2, wherein 0.98 × Rlc ≧ Ral1 ≧ Ral2. 4. The liquid crystal display device according to claim 1, wherein the alignment film contains conductive particles. 5. The conductive particles are one or more of indium oxide, tin oxide, indium tin oxide, cadmium-doped tin oxide, titanium oxide, titanium dioxide and zinc oxide. 4. The liquid crystal display device according to item 4. 6. The liquid crystal display device according to claim 1, wherein the alignment film contains a metal alkoxide. 7. The liquid crystal display device according to claim 1, wherein the liquid crystal display system is an IPS system. 8. The liquid crystal display device according to claim 1, wherein the liquid crystal display system is a vertical alignment system. 9. A low temperature polycrystalline silicon TFT or a continuous grain boundary crystalline silicon TFT is used.
9. The liquid crystal display device according to any one of items 8 to 8. 10. The liquid crystal display device according to claim 1, wherein at least one of the two liquid crystal display device substrates is a color filter substrate having colored pixels. 11. The liquid crystal display device according to claim 10, wherein the color filter substrate has a frame or a black matrix, and the frame or the black matrix is a resin containing a pigment. 12. The liquid crystal display device according to claim 11, wherein the pigment constituting the frame or the black matrix is a metal oxide. 13. The liquid crystal display device according to claim 12, wherein the metal oxide contains at least titanium oxynitride.