JPH07191323A - Substrate for liquid crystal panel and its manufacture - Google Patents

Abstract

PURPOSE:To widen the visual field angle of a TN type liquid crystal panel. CONSTITUTION:Pixel electrodes are coated with a 1st orientation film 51, whose surface is fluoridated (61); and a 2nd orientation film 52 is selectively formed. Thus, the top surface of the 1st orientation film 51 is fluoridated and then the 2nd orientation film 52 is formed, so chemical resistance of photosensitive resin, used for the selective formation of the 1st orientation film 51, to a developer and peeling liquid is improved to obtain multiple domains without deteriorating characteristics of the orientation films, thereby widening the visual field angle.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal panel having an image display function, and more particularly to a structure of an alignment film which is effective in a liquid crystal image display device using a TN type liquid crystal material and a manufacturing method thereof.

[0002]

2. Description of the Related Art Due to recent advances in microfabrication technology, liquid crystal materials, packaging technology, etc., television images and various image displays, which are about 3 to 15 inches in size, can be used practically on liquid crystal panels on a commercial basis. Already obtained. Color display can be easily realized by forming an RGB colored layer on one of the two glass substrates constituting the liquid crystal panel, and a switching element is incorporated for each pixel.
In the so-called active type liquid crystal panel, an image having a small crosstalk and a high contrast ratio is guaranteed.

In such a liquid crystal panel, a matrix organization of 120 to 960 as scanning lines and 240 to 2000 as signal lines is standard, and one of the liquid crystal panels 1 is constructed as shown in FIG. A COG (Chip-On-Glass) method in which a semiconductor integrated circuit chip 3 for supplying a drive signal is directly connected to a transparent insulating substrate, for example, an electrode terminal group 6 of scanning lines formed on a glass substrate 2, or a polyimide-based method, for example. The electrical signal is imaged by a mounting means such as a method of fixing the connection film 4 having a terminal group (not shown) of a copper foil plated with gold based on a resin thin film with the electrode terminal group 5 of the signal line while being pressed with an adhesive. It is supplied to the display unit. Here, for convenience, two mounting methods are illustrated at the same time, but it goes without saying that either mounting method is actually selected. Numerals 7 and 8 are wiring paths for connecting between the image display section in the center of the liquid crystal panel 1 and the electrode terminal groups 5 and 6 of the signal line and the scanning line, and are made of the same conductive material as the electrode terminal groups 5 and 6. No need to be done.

Reference numeral 9 is another glass substrate having a transparent conductive counter electrode common to all liquid crystal cells, and two glass substrates 2 and 9 are each several μm in size by a spacer such as quartz fiber or plastic beads. Are separated by a predetermined distance, and the gap is a closed space sealed by a sealing material made of an organic resin and a sealing material, and the closed space is filled with liquid crystal. In order to realize color display, an organic thin film containing one or both of a dye and a pigment called a coloring layer is attached to the closed space side of the glass substrate 9 to provide a color display function. In that case, The glass substrate 9 is also called a color filter. Depending on the properties of the liquid crystal material, a polarizing plate is attached to either the upper surface of the glass substrate 9 or the lower surface of the glass substrate 2 or both surfaces, and the liquid crystal panel 1 functions as an electro-optical element.

FIG. 11 is an equivalent circuit diagram of an active liquid crystal panel in which an insulated gate transistor 10 is arranged as a switching element for each picture element. The element drawn by the solid line is formed on one glass substrate 2, and the element drawn by the broken line is formed on the other glass substrate 9. Scan line 1
1 (8) and the signal line 12 (7) have, for example, amorphous silicon (a-Si) as a semiconductor layer and a silicon nitride layer (SiN).
TFT (thin film transistor) whose gate insulating layer is _X )
It is formed on the glass substrate 2 simultaneously with the formation of 10. The liquid crystal cell 13 includes a transparent conductive pixel electrode 14 formed on the glass substrate 2, a transparent conductive counter electrode 15 formed on the glass substrate 9 which is a color filter, and two glass substrates 2 , 9 and a liquid crystal that fills the closed space and is electrically treated like a capacitor.
Several choices can be made regarding the configuration of the storage capacitor. For example, in FIG. 11, the storage capacitor 22 is the gate (scan line) of the preceding stage.
And the picture element electrode 14.

FIG. 12 is a sectional view of the main part of a color liquid crystal image display device. As described above, the colored layer 18 made of the dyed photosensitive gelatin or the colored photosensitive resin is provided on the closed space side of the glass substrate 9 which is the color filter.
4 are arranged according to a predetermined arrangement in the three primary colors of RGB. Counter electrode 15 common to all pixel electrodes 14
Is formed on the coloring layer 18 as shown in order to avoid a voltage distribution loss due to the presence of the coloring layer 18. Liquid crystal 16
A polyimide resin thin film layer 19 having a film thickness of, for example, about 0.1 μm, which is deposited on the two glass substrates 2 and 9 in contact with
Is an alignment film for aligning liquid crystal molecules in a predetermined direction. In addition, when the twisted nematic (TN) type liquid crystal 16 is used, two polarizing plates 20 are required above and below.

When a low-reflectivity opaque film 21 is arranged at the boundary of the RGB colored layers 18, the signal lines 12 on the glass substrate 2 are arranged.
The light reflected from the wiring layer such as the above can be prevented, the contrast ratio can be improved, and the thin film transistor (switching element) 1
It is possible to prevent an increase in leak current at the time of turning off due to external light irradiation of 0, and it is possible to operate even under strong external light, which is put to practical use as a black matrix. Although many configurations of the black matrix material are possible, a Cr thin film having a film thickness of about 0.1 μm is simple, though it is costly, considering the occurrence of a step at the boundary of the colored layer and the light transmittance.

Note that, in order to facilitate understanding in FIG. 12, in addition to the thin film transistor 10, the scanning line 11, and the storage capacitor 22, main factors such as a backlight light source and a spacer are omitted. Reference numeral 23 is a conductive thin film for connecting the pixel electrode 14 and the drain of the thin film transistor 10 and is generally formed of the same material as the signal line 12 at the same time. Although not shown here, the counter electrode 15 is connected to an appropriate conductive pattern on the glass substrate (TFT substrate) 2 through an appropriate conductive paste at a corner slightly outside the image display portion, It is incorporated in a part of the electrode terminal groups 5 and 6 to provide electrical connection.

FIG. 13 is a conceptual diagram showing the direction of the alignment treatment for the two glass substrates 2 and 9 coated with the alignment film 19. Both of the glass substrates 2 and 9 have the main surface coated with the alignment film. It is displayed on the page. A polyimide resin is generally used for the alignment film 19 from the viewpoint of heat resistance,
0. only in the area (image display area) required for offset printing.
It is applied in a film thickness of about 1 μm and heat-cured by heat treatment at 150 to 300 ° C. When the liquid crystal material is TN type, the glass substrate 2 is attached to the rotary drum around which the dry cloth is wound.
Alignment treatment is carried out by pressing and sliding 9 under suitable pressure so that the moving directions 30-1 and 30-2 thereof are substantially orthogonal to each other.

FIG. 14 (a) shows a cross-sectional view of the main part of a conventional liquid crystal panel. Here, a cross-sectional view is shown in which the normally white operation mode is selected and the polarizing plate is omitted. The angle formed by the incident light 31 with the alignment direction of the liquid crystal molecules 32 is almost the same regardless of the incident angle of the incident light 31 in the all-white display, but in the halftone display, it largely differs depending on the incident angle, and as a result, as shown in FIG. As shown in b), the transmittance of the liquid crystal panel has an angle dependence in the vertical direction, and depending on the viewing angle, undesired phenomena such as deterioration of contrast and color reversal of the displayed image are observed. The corners feel narrow.

On the other hand, as shown in FIG. 15 (a), it is possible to perform an alignment treatment such that the liquid crystal array directions are opposite to each other in the pair of picture element electrodes 14 and 15 33 and 34. In the halftone display, the incident light 31 causes the liquid crystal alignment direction 33,
The angle formed with 34 is symmetrical, and as a result, FIG.
As shown in (1), the angle dependence of the transmittance in the vertical direction is greatly alleviated, and the viewer perceives a wide viewing angle.

The liquid crystal cell structure in which the arrangement of the liquid crystal molecules in one set of pixel electrodes is reversed is called a multi-domain, and different alignment treatments are applied to the alignment films on one set of pixel electrodes. There is a need. FIG. 16 shows an example of a method for realizing the above multi-domain. Although the pixel electrodes and other components are omitted, first, as shown in FIG. 16A, an alignment film 19 is applied on the glass substrate 2 and heat-cured appropriately.
Next, as shown in FIG. 16 (b), the rotary drum 35 wound with the dry cloth is slid while being pressed against the alignment film 19 by the left rotation 36 at an appropriate pressure and rotation speed. As shown in FIG. After that, as shown in FIG. 16D, the alignment film 19 is selectively covered with a predetermined pattern by, for example, a photosensitive resin 38 as a member having an appropriate mask function. Then, as shown in FIG. 16E, the rotating drum 35 is rotated rightward 39 to form the alignment film 19.
16 while sliding while pressing it at an appropriate pressure and rotation speed,
As shown in (f), a pretilt angle 40 rising to the left is obtained in the exposed alignment film 19. Finally, if the photosensitive resin 38 is removed as shown in FIG.
Is an alignment film 19-having a pretilt angle of 37
Alignment film 19 having pretilt angle 40 of 1 and rising to the left
It will be understood that it is divided into -2 and.

[0013]

In the above-mentioned multi-domain, the greatest problem is the method of removing the photosensitive resin that exhibits the selective mask function during the second alignment treatment. This is because the alignment film is a heat-resistant polyimide-based resin, but the heat resistance of the colored layer that constitutes the color filter is low, and currently a color filter exceeding 250 ° C. is under development. Since the heat resistance of the TFT substrate that constitutes it is at most 300 ° C,
In practice, the curing temperature of the alignment film is about 200 ° C. to 250 ° C. Therefore, the chemical resistance of the alignment film is weak and it is a stripper or organic solvent that removes the photosensitive resin. . For this reason, even though it is possible to form multi-domains, only the liquid crystal panel having the alignment performance deteriorated to lower the contrast of the displayed image and the long-term reliability is not obtained.

On the other hand, the above-mentioned problems do not occur with a water-soluble photosensitive resin which does not use an organic solvent as a diluting solution, but the water-soluble photosensitive resin has drawbacks in sensitivity and resolution, and is difficult to use in semiconductors and liquid crystal devices. Very rarely used for microfabrication. An object of the present invention is to provide a liquid crystal panel substrate and a method for manufacturing the same, which can reduce the number of manufacturing steps.

Another object of the present invention is to provide a liquid crystal panel substrate which does not damage the alignment film and a method of manufacturing the same.

[0016]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and the selection of an alignment film by a fluorination treatment and lift-off for imparting chemical resistance to the removal of a photosensitive resin to the alignment film. Formation is the core. The method for manufacturing a liquid crystal panel substrate according to claim 1, wherein the first alignment film is formed on the transparent conductive pixel electrode formed on the transparent insulating substrate, and the first alignment film is partially formed on the first alignment film. A second alignment film having a pretilt angle different from that of the first alignment film is formed, and the second alignment film is unnecessary with a developer of a positive photosensitive resin used for selective pattern formation of the second alignment film. Remove the part.

According to a second aspect of the present invention, there is provided a liquid crystal panel substrate, wherein a first alignment film having a partially fluorinated surface is formed on a transparent conductive pixel electrode on a transparent insulating substrate. A second alignment film having a pretilt angle different from that of the first alignment film is formed on the fluorinated portion of the first alignment film which is fluorinated. The method for manufacturing a liquid crystal panel substrate according to claim 3, wherein a first alignment film is formed on a transparent conductive pixel electrode formed on a transparent insulating substrate, and then the surface of the first alignment film is formed. Then, a second alignment film having a pretilt angle different from that of the first alignment film is applied onto the fluorinated first alignment film, and then a positive photosensitive resin is applied onto the second alignment film. After coating, the pixel electrodes are selectively exposed to light, and then the photosensitive resin after exposure is developed and the second alignment film is selectively removed to expose the first alignment film, and then the photosensitivity is set. The resin is removed, and then the fluorinated surface on the first alignment film exposed by the oxygen gas plasma is removed.

According to a fourth aspect of the present invention, there is provided a method of manufacturing a liquid crystal panel substrate, wherein a first alignment film is applied on a transparent conductive pixel electrode formed on a transparent insulating substrate, and then the first alignment film is formed. The surface of the first alignment film is fluorinated, then a second alignment film having a pretilt angle different from that of the first alignment film is applied onto the fluorinated first alignment film, and then the surface of the second alignment film is fluorinated. Then, a positive photosensitive resin is applied on the fluorinated second alignment film, and then the inside of the pixel electrode is selectively exposed, and then the exposed photosensitive resin is developed to selectively remove the second photosensitive resin. Exposing the first alignment film by exposing the first alignment film, and then removing the fluorinated surface on the second alignment film exposed by the oxygen gas plasma, and then selectively removing the second alignment film. Then, the photosensitive resin was removed, and then the first exposed by oxygen gas plasma.
And removing the fluorinated surface on the second alignment film.

According to a fifth aspect of the present invention, in the liquid crystal panel substrate, the first alignment film and the first alignment film have different pretilt angles on the transparent conductive pixel electrode formed on the transparent insulating substrate. The second alignment film is formed adjacently. The method for manufacturing a substrate for a liquid crystal panel according to claim 6, wherein a first alignment film is applied on a transparent conductive pixel electrode formed on a transparent insulating substrate, and then lift-off is performed on the first alignment film. Then, a layer of the lift-off layer and the first alignment film is selectively left on the pixel electrode by using a photosensitive resin, and then the first alignment film having a different pretilt angle is used. No. 2 alignment film is applied, and then the thickness of the second alignment film is reduced by oxygen gas plasma to expose the side surface of the laminated portion, and then the lift-off layer is removed and the second alignment film on the lift-off layer is removed. Remove.

A method of manufacturing a liquid crystal panel substrate according to a seventh aspect is the method of manufacturing a liquid crystal panel substrate according to the sixth aspect, wherein the lift-off layer is molybdenum, and the lift-off layer removing liquid is hydrogen peroxide or dilute nitric acid. is there. The method for producing a substrate for a liquid crystal panel according to claim 8 is the method for producing a substrate for a liquid crystal panel according to claim 6, wherein a negative type is used as the photosensitive resin, the lift-off layer is a PVA resin, and the removing liquid for the lift-off layer is It is water.

According to a ninth aspect of the present invention, there is provided a method for manufacturing a liquid crystal panel substrate, in which a first alignment film is applied on a transparent conductive pixel electrode formed on a transparent insulating substrate, and then the first alignment film is applied. A lift-off layer is deposited on top, then a photosensitive resin is applied on the lift-off layer, and then a laminated portion composed of the photosensitive resin, the lift-off layer and the first alignment film is selectively left on the pixel electrode, Then, a second alignment film having a pretilt angle different from that of the first alignment film is applied, and then the thickness of the second alignment film is reduced by oxygen gas plasma to expose the side surface of the laminated portion, and then the lift-off layer is formed. At the same time as the removal, the photosensitive resin and the second alignment film on the lift-off layer are removed.

A method for manufacturing a liquid crystal panel substrate according to a tenth aspect is the method for manufacturing a liquid crystal panel substrate according to the ninth aspect, wherein the lift-off layer is molybdenum, and the lift-off layer removing liquid is hydrogen peroxide or dilute nitric acid. is there. The method for producing a substrate for a liquid crystal panel according to claim 11 is the method for producing a substrate for a liquid crystal panel according to claim 9, wherein a negative type is used as the photosensitive resin, the lift-off layer is a PVA resin, and the removing liquid for the lift-off layer is It is water.

According to a twelfth aspect of the present invention, in the method for manufacturing a liquid crystal panel substrate, the first alignment film is applied on the transparent conductive pixel electrode formed on the transparent insulating substrate, and then the first alignment film is formed. Of the first alignment film having a pretilt angle different from that of the first alignment film, and the first alignment film other than the first alignment film is fluorinated. The area is filled and then the fluorinated surface on the first alignment film is removed by oxygen gas plasma.

[0024]

According to the structure of claim 1, the second alignment film can be removed in the same step as the photosensitive resin with the developing solution of the photosensitive resin,
Fewer steps are required. In the structure according to any one of claims 2 to 12, when the alignment film is formed by fluorination, the alignment film having a fluorinated surface has remarkably improved water repellency and chemical resistance, and is resistant to the developing solution of the photosensitive resin. It is avoided that the film is thinned. Further, in forming the alignment film by lift-off, the alignment film is protected by the lift-off layer, and is never damaged by the photosensitive resin removing liquid.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT An embodiment of the present invention will be described below with reference to the manufacturing process sectional views of FIGS. For the sake of convenience, the same parts are designated by the same reference numerals as in the conventional example. [First Embodiment] In the first embodiment of the present invention corresponding to claim 1, first, as shown in FIG. 1 (a), a transparent film having a pixel electrode (not shown) is formed. The first alignment film 51 is formed on the insulating substrate, for example, the glass substrate 2 by 0.1
It is applied to a film thickness of about μm and thermally cured at 220 ° C. for about 1 hour. As the first alignment film 51, a thermosetting polyimide resin, for example, RN740 manufactured by Nissan Chemical is selected.

Subsequently, as shown in FIG. 1B, the second alignment film 52 is applied on the first alignment film 51 to a film thickness of about 0.1 μm and heat-treated at 170 ° C. for about 30 minutes. To evaporate the solvent. As the second alignment film 52, a pleimide type polyimide resin, for example, Optomer A made by Japan Synthetic Rubber
L3046 is selected. After that, as shown in FIG. 1C, a positive photosensitive resin 53, for example, TF manufactured by Tokyo Ohka
RB is applied to a film thickness of about 1 μm, prebaked at 100 ° C. for about 10 minutes, and selectively exposed to ultraviolet light by the photomask 54 and the ultraviolet light 55.

Then, when the developing treatment is performed with a TMAH aqueous solution having a concentration of 2.38% as the developing solution, the developing solution is alkaline, so that the photosensitive resin 5 as shown in FIG.
In both cases 3, the second alignment film 52 is patterned to form the photosensitive resin pattern 53 'and the second alignment film pattern 52' at the same time, and the number of steps can be reduced. However, it is necessary to take care not to reduce the thickness of the first alignment film 51 due to overdevelopment. After this, unnecessary photosensitive resin pattern 53 '
Can be removed, and by using an organic solvent such as acetone, IPA, or MEK, damage to the first alignment film 51 can be minimized.

Finally, as shown in FIG. 1E, the glass substrate 2 in which the second alignment film 52 'is selectively formed on the first alignment film 51 is obtained. The liquid crystal panel substrate obtained according to the first embodiment has two kinds of alignment films 51 and 52 'in a unit pixel, and an alignment of liquid crystal molecules similar to that shown in FIG. 15A is obtained. In order to expand the viewing angle, it is necessary to devise a structure as shown in FIG. Specifically, the third alignment film 19 formed on one glass substrate 9
A second alignment film 52 ′ having a larger pretilt angle than
On the contrary, the first alignment film 51 whose pretilt angle is smaller than that of the third alignment film 19 is selected.

In the above construction, one glass substrate 9 is subjected to an alignment treatment so as to have a pretilt angle θ, and the other glass substrate 2 is subjected to a pretilt angle of θ + φ1 and a pretilt angle of θ−φ2 (however, φ1 > 0, θ>φ2> 0)
It has two orientation processing regions. When such an alignment treatment is performed, the liquid crystal molecules in the central portion of the liquid crystal layer have a pretilt of about φ1 in the area having a pretilt angle of θ + φ1 and the liquid crystal molecules in the central portion of the liquid crystal layer in the area having a pretilt angle of θ−φ2. Are oriented to have a pretilt of approximately -φ2. As a result, even in the halftone display, the angle formed by the incident light 31 (see FIG. 15A) and the two kinds of alignment directions of the liquid crystal is symmetrical, and the vertical dependence of the transmittance on the vertical direction is significantly reduced. , The viewing angle is expanded. When φ1 = φ2, the molecular arrangement most similar to that shown in FIG. Arranging two kinds of alignment films in the unit picture element in this way is the main point of expanding the viewing angle, and the description of other examples will be continued.

In the first embodiment of the present invention, the first alignment film is liable to be thinned due to overdevelopment, and not only the process requires careful attention, but also the combustible resin for removing the photosensitive resin pattern. Since a volatile organic solvent is used, safety measures and environmental measures are essential. Therefore, in the second and subsequent examples, examples will be described in which the film loss of the alignment film is prevented and the photosensitive resin pattern is safely removed.

According to a second aspect of the present invention, a first alignment film whose surface is partially fluorinated is formed on a transparent insulating substrate, and a first alignment film is partially formed on the partially fluorinated first alignment film. A method of manufacturing a substrate for a liquid crystal panel in which the second alignment film is formed in a self-aligning manner, and it becomes possible to improve the chemical resistance of the alignment film by fluorinating at least the surface of the first alignment film. The feature is that it is not necessary to use an organic solvent for removing the photosensitive resin and the second alignment film. Two production methods can be selected depending on the number of fluorinations, which will be described below as second and third embodiments.

[Second Embodiment] In the second embodiment of the present invention, first, as shown in FIG. 3A, a transparent insulating substrate on which a pixel electrode (not shown) is formed is used. For example, the first alignment film 51 is applied on the glass substrate 2 with a film thickness of about 0.1 μm, and is thermally cured at 220 ° C. for about 1 hour. As the first alignment film 51, RN740 manufactured by Nissan Chemical Industries, Ltd. is selected. Then, the surface of the first alignment film 51 is fluorinated by a fluorine gas plasma 56 under a reduced pressure using a Freon-based gas, for example, CF ₄ , to a fluorinated portion 61 of about 50 to 150 Å.

Subsequently, as shown in FIG. 3B, the second alignment film 52 is applied on the first alignment film 51 to a film thickness of about 0.1 μm and heat-treated at 170 ° C. for about 30 minutes. . As the second alignment film 52, Optomer AL3 made by Japan Synthetic Rubber is used.
046 is selected. If the second alignment film 52 is repelled upon application of the second alignment film 52, there is no problem even if it is applied using an appropriate adhesion enhancing material such as HMDS.

After that, as shown in FIG. 3C, a positive type photosensitive resin 53 is applied to a film thickness of about 1 μm, and 100
Prebaking is performed at 10 ° C. for about 10 minutes, and selective photo-irradiation with the photo mask 54 and the photo-UV 55 is performed. Then, when the developing treatment is performed with a TMAH aqueous solution having a concentration of 2.38% as the developing solution, the developing solution is alkaline, so that the photosensitive resin 53 and the second alignment film 52 as shown in FIG. 3D are used.
Are patterned to obtain a photosensitive resin pattern 53 'and a second alignment film pattern 52' at the same time. During the development process, the surface of the first alignment film 51 is fluorinated, and therefore the first alignment film 51 is never thinned.

After that, unnecessary photosensitive resin pattern 53 'is formed.
Is removed, and as shown in FIG.
The photosensitive resin pattern 53 'can be easily removed by irradiating the entire surface with 5 and developing it again. However, if the overdevelopment is not taken into consideration during the redevelopment, the film thickness of the second alignment film 52 ′ is reduced. Then, as shown in FIG. 3F, the fluorinated portion 61 ′ on the surface of the first alignment film 51 is ashed by the treatment in the oxygen gas plasma 57 to expose the first alignment film 51. At this time, the second alignment film 52 'is also partially thinned, but finally, as shown in FIG. 3G, the first alignment film 51 whose surface is partially fluorinated is formed. A liquid crystal panel substrate is obtained in which a second alignment film 52 'is formed in a self-aligned manner on the formed and partially fluorinated first alignment film 51.

[Third Embodiment] In the third embodiment of the present invention, the process is improved so that the second alignment film is not thinned during the removal of the photosensitive resin in the second embodiment. First, as shown in FIG. 4A, although not shown, a first alignment film 51 having a thickness of about 0.1 μm is formed on a transparent insulating substrate, for example, a glass substrate 2 on which pixel electrodes are formed. It is applied thickly and is heat-cured at 220 ° C. for about 1 hour. First
RN740 manufactured by Nissan Kagaku Co., Ltd. is selected as the alignment film 51. Then, the surface of the first alignment film 51 is fluorinated by a fluorine gas plasma 56 under reduced pressure using CF ₄ to a fluorinated portion 61 by about 50 to 150 Å.

Subsequently, as shown in FIG. 4B, the second alignment film 52 is applied on the first alignment film 51 to a film thickness of about 0.1 μm and heat-treated at 170 ° C. for about 30 minutes. . As the second alignment film 52, Optomer AL3 made by Japan Synthetic Rubber is used.
046 is selected. It has already been described that there is no problem even if a suitable adhesion enhancing material such as HMDS is used for applying the second alignment film 52. After applying the second alignment film 52, the fluorine gas plasma 5 under reduced pressure using CF ₄ again is used.
6, the surface of the second alignment film 52 is also fluorinated by about 50 to 150Å to form a fluorinated portion 62.

Thereafter, as shown in FIG. 4 (c), a positive type photosensitive resin 53 is applied to a film thickness of about 1 μm and 100
Prebaking is performed at 10 ° C. for about 10 minutes, and selective photo-irradiation with the photo mask 54 and the photo-UV 55 is performed. Then, by performing development processing with a TMAH aqueous solution having a concentration of 2.38% as a developing solution, a photosensitive resin pattern 53 ′ can be obtained as shown in FIG. 4 (d).

Since the surface of the second alignment film 52 is fluorinated, the fluorinated portion 62 fluorinated in oxygen gas plasma is ashed to expose the second alignment film 52, and then, as shown in FIG.
As shown in (e), the development process or the second alignment film 52 is performed.
Selective pattern formation of the second alignment film 52 is performed with the diluent. At the time of selectively removing the second alignment film 52, the surface of the first alignment film 51 is fluorinated, so that the first alignment film 51 is removed.
There is no reduction in film thickness. After that, the unnecessary photosensitive resin pattern 53 'may be removed, and the photosensitive resin pattern 53' can be easily removed by irradiating the entire surface with the ultraviolet ray 55 and performing the developing process again as in the second embodiment. To be done. Even if overdevelopment is given at the time of redevelopment, since the surface of the second alignment film 52 'is also fluorinated, the film thickness of the second alignment film 52' does not decrease.

Then, the fluorinated portions 61 and 62 on the surfaces of the first alignment film 51 and the second alignment film 52 'are simultaneously ashed by a treatment in oxygen gas plasma, and finally, as shown in FIG.
As shown in FIG. 3, the first alignment film 51 whose surface is partially fluorinated is formed on the glass substrate 2, and the second alignment film 51 is partially fluorinated on the first alignment film 51. Alignment film 52 '
Thus, a liquid crystal panel substrate having a self-aligned structure is obtained.

According to a fifth aspect of the present invention, the first alignment film and the second alignment film are formed adjacent to each other on the transparent conductive pixel electrode formed on the transparent insulating substrate. A substrate for a liquid crystal panel characterized by claim 6 is a manufacturing method characterized by forming a second alignment film by lift-off of the substrate. There are two types of manufacturing methods depending on the selection of the lift-off material, which will be described below as the fourth and fifth embodiments.

[Fourth Embodiment] In the fourth embodiment of the present invention, as shown in FIG. 5A, a transparent insulating substrate on which a pixel electrode (not shown) is formed is formed. For example, the first alignment film 51 is applied on the glass substrate 2 with a film thickness of about 0.1 μm, and is thermally cured at 220 ° C. for about 1 hour. As the first alignment film 51, RN740 manufactured by Nissan Chemical Industries, Ltd. is selected. Subsequently, Mo (molybdenum) is used as the lift-off layer 63 on the entire surface by using a vacuum film-forming apparatus such as sputtering.
Positive type photosensitive resin 5 with a film thickness of about μm
3 is applied to a film thickness of about 1 μm and prebaked at 100 ° C. for about 10 minutes.

After that, selective exposure is carried out by photomask and ultraviolet irradiation to obtain a predetermined photosensitive resin pattern 53 'as shown in FIG. 5B, and the photosensitive resin pattern 5 is obtained.
The lift-off layer (Mo layer) 63 and the first layer 3'are used as a mask.
The alignment film 51 is etched to form 63 'and 51', respectively. The etching method may be a general etching method and is not particularly limited. For example, the lift-off layer 63 is formed by dry etching using a Freon-based gas, and the first alignment film 51 is formed by ashing using an oxygen gas plasma. By etching, there is the convenience that one processing device can be used in time. The method of removing the photosensitive resin pattern 53 ′ is not particularly limited because the first alignment film 53 ′ is covered by the lift-off layer 63 ′, and after the first alignment film 51 is etched, oxygen is directly used. It is also possible to remove by gas plasma.

After removing the photosensitive resin pattern 53 ', FIG.
The second alignment film 52 is formed on the glass substrate 2 as shown in FIG.
A film having a film thickness of about 0.1 μm is applied on the top and heat-treated at 170 ° C. for about 30 minutes. As the second alignment film 52, Optomer AL3046 made by Japan Synthetic Rubber is selected. And FIG.
As shown in (d), the film thickness of the second alignment film 52 is reduced so that the second alignment film 52 is stepped in the step portion of the laminated pattern composed of the lift-off layer 63 ′ and the first alignment film 51 ′. Oxygen gas plasma 5 until breakage occurs and the side surface of the laminated part is exposed
The process in 7 is performed.

The final step is to remove the lift-off layer 63 'and selectively remove the second alignment film 52 on the lift-off layer 63'. Dilute nitric acid of about 1% is used. Unlike the developing solution for the photosensitive resin 53, these removing solutions are neutral or weak acids, so that the first and second alignment films 51 ', 5'
There is no danger of 2's being attacked and film loss. As a result, as shown in FIG. 5E, the first alignment film 51 ′ and the second alignment film 51 ′ are formed on the transparent conductive pixel electrode formed on the glass substrate 2 which is the transparent insulating substrate. And 52 'could be formed adjacent to each other.

[Fifth Embodiment] In the fifth embodiment of the present invention, a lift-off material which does not require an expensive vacuum film forming apparatus is adopted. First, as shown in FIG. 6 (a). Although not shown, a first alignment film 51 having a thickness of about 0.1 μm is applied on a transparent insulating substrate, for example, a glass substrate 2 on which pixel electrodes are formed, and heat is applied at 220 ° C. for about 1 hour. Harden. As the first alignment film 51, RN manufactured by Nissan Chemical Co., Ltd.
740 is selected. Subsequently, a water-soluble PVA resin such as TPF manufactured by Tokyo Ohka Co., Ltd. is used as the lift-off layer 64 in an amount of 0.1 μm.
It is applied to a film thickness of about m and heated at 140 ° C. for 10 minutes, and a negative photosensitive resin 65, for example, OM manufactured by Tokyo Ohka
R-83 is applied to a film thickness of about 1 μm and prebaked at 90 ° C. for about 5 minutes.

After that, by performing selective exposure by photomask and ultraviolet irradiation, and developing, a predetermined photosensitive resin pattern 65 'is obtained as shown in FIG. 6 (b). During the development of the negative resist, the lift-off layer (TPF layer) 64 is insoluble in an organic solvent such as xylene which is a developer or butyl acetate which is a rinse solution, and therefore the lift-off layer 64 is not thinned.

The lift-off layer 64 and the first alignment film 51 are etched by using the photosensitive resin pattern 65 'as a mask, as shown in FIG.
As shown in (c), they are 64 'and 51', respectively.
As an etching method, since the object is an organic thin film, if the lift-off layer 64 and the first alignment film 51 are etched by ashing using oxygen gas, there is the convenience that only one processing apparatus is enough. The method for removing the photosensitive resin pattern 65 'is such that the first alignment film 51' is covered with the lift-off layer 64 ', so that a negative photosensitive resin stripper containing ABS (alkylbenzene sulfonic acid) as a main component is used. Since the lift-off layer 64 ′ is also insoluble in the stripping solution without any trouble, the lift-off layer 64 ′ is not thinned.

After removing the photosensitive resin pattern 65 ', FIG.
As shown in (d), the second alignment film 52 is formed on the glass substrate 2
A film having a film thickness of about 0.1 μm is applied on the top and heat-treated at 170 ° C. for about 30 minutes. As the second alignment film 52, Optomer AL3046 made by Japan Synthetic Rubber is selected. And FIG.
As shown in (e), the film thickness of the second alignment film 52 is reduced so that the second alignment film 52 is stepped at the step portion of the stacked pattern including the lift-off layer 64 ′ and the first alignment film 51 ′. Oxygen gas plasma 5 until breakage occurs and the side surface of the laminated part is exposed
The process in 7 is performed.

The final step is to remove the lift-off layer 64 'and also selectively remove the second alignment film 52 on the lift-off layer 64'. Water is used to remove the lift-off layer 64 '. Since water is neutral unlike the developing solution of the photosensitive resin, there is no possibility that the first and second alignment films 51 'and 52' will be attacked and the film will be reduced. As a result, FIG.
As shown in (f), the first alignment film 51 'and the second alignment film 52' are adjacent to each other on the transparent conductive pixel electrode formed on the glass substrate 2 which is a transparent insulating substrate. Could be formed.

The ninth aspect of the present invention is also a manufacturing method characterized by forming the second alignment film by lift-off of the same substrate, but the number of manufacturing steps can be reduced as compared to the sixth aspect, and similarly. Two types of manufacturing methods have been devised by selecting the lift-off material, which will be described below as sixth and seventh embodiments. [Sixth Embodiment] In the sixth embodiment of the present invention,
First, as shown in FIG. 7A, although not shown, a first alignment film 51 having a film thickness of about 0.1 μm is formed on a transparent insulating substrate, for example, a glass substrate 2 on which pixel electrodes are formed. And then heat-cured at 220 ° C. for about 1 hour. First alignment film 5
RN740 manufactured by Nissan Kagaku is selected as 1. Subsequently, Mo (molybdenum) is deposited as the lift-off layer 63 on the entire surface to a thickness of about 0.1 μm by using a vacuum film-forming apparatus such as sputtering, and then the positive photosensitive resin 53 is applied to a thickness of about 1 μm. Then, prebaking is performed at 100 ° C. for about 10 minutes.

After that, selective exposure is performed by photomask and ultraviolet irradiation to obtain a predetermined photosensitive resin pattern 53 'as shown in FIG. 7B, and the photosensitive resin pattern 53' is obtained.
Using the as a mask, the lift-off layer 63 and the first alignment film 51 are etched to form 63 ′ and 51 ′, respectively. As described above, as the etching method, if the lift-off layer 63 is etched by dry etching using a Freon-based gas, and the first alignment film 51 is etched by ashing using oxygen gas plasma,
There is the convenience that only one processing device is needed.

Subsequently, as shown in FIG. 7C, the second alignment film 52 is applied on the glass substrate 2 to a film thickness of about 0.1 μm and heat-treated at 170 ° C. for about 30 minutes. As the second alignment film 52, Optomer AL304 made by Japan Synthetic Rubber is used.
6 is selected. First alignment film 51 'and lift-off layer 63'
Since the film thickness of the three-layered photosensitive resin pattern 53 ′ is 1.2 μm, the second alignment film 52 is likely to be broken on the side surface of the multilayered part.

Therefore, the lift-off layer 63 may be immersed as it is in a Mo removing solution, but if reliability is desired, as shown in FIG. 7D, as in the fifth and sixth embodiments. In addition, it is advisable to add a treatment in the oxygen gas plasma 57 to promote the exposure of the side surface of the laminated portion. The final step is to remove the lift-off layer 63 ′ and selectively remove the photosensitive resin pattern 53 ′ and the second alignment film 52 on the lift-off layer 63 ′. The removal of the lift-off layer 63 ′ is described above. As described above, hydrogen peroxide water or dilute nitric acid of about 0.1% is used. As a result, as shown in FIG. 7E, the first alignment film 51 ′ and the second alignment film 51 ′ are formed on the transparent conductive pixel electrode formed on the glass substrate 2 which is the transparent insulating substrate. 5
2'can be formed adjacently.

[Seventh Embodiment] In the seventh embodiment of the present invention, first, as shown in FIG. 8A, a transparent insulating substrate having a pixel electrode (not shown) is formed. For example, the first alignment film 51 is applied on the glass substrate 2 with a film thickness of about 0.1 μm, and is thermally cured at 220 ° C. for about 1 hour. As the first alignment film 51, RN740 manufactured by Nissan Chemical Industries, Ltd. is selected. Subsequently, a water-soluble PVA resin such as TPF manufactured by Tokyo Ohka Co., Ltd. is applied to the entire surface as the lift-off layer 64 in a film thickness of about 0.1 μm and heated at 140 ° C. for 10 minutes, and a negative photosensitive resin 65 such as Tokyo. Oka-8 made by Oka
3 is applied in a film thickness of about 1 μm and prebaked at 90 ° C. for about 5 minutes.

After that, selective exposure is performed by photomask and ultraviolet irradiation to develop, and as shown in FIG.
A photosensitive resin pattern 65 'is obtained. The lift-off layer 64 and the first alignment film 51 are etched by using the photosensitive resin pattern 65 ′ as a mask to form 64 ′, 5 as shown in FIG. 8B.
Get 1 '. As a method of etching, if the lift-off layer 64 and the first alignment film 51 are etched by ashing using oxygen gas, there is the convenience that only one processing apparatus is enough.

Subsequently, as shown in FIG. 8C, the second alignment film 52 is applied on the glass substrate 2 to a film thickness of about 0.1 μm and heat-treated at 170 ° C. for about 30 minutes. As the second alignment film 52, Optomer AL304 made by Japan Synthetic Rubber is used.
6 is selected. First alignment film 51 'and lift-off layer 6
Since the laminated portion composed of three layers of 4'and the photosensitive resin pattern 65 'has a film thickness of 1.2 μm, the second alignment film 52 is likely to be discontinuous on the side surface of the laminated portion.

Therefore, the lift-off layer 64 may be immersed in the TPF removing solution as it is, but if the reliability is desired, as shown in FIG. 8D, as in the fifth and sixth embodiments. In addition, it is advisable to add a treatment in the oxygen gas plasma 57 to promote the exposure of the side surface of the laminated portion. The final step is to remove the lift-off layer 64 'and selectively remove the second photosensitive resin pattern 65' and the second alignment film 52 on the lift-off layer 64 '. Use water.

As a result, as shown in FIG. 8 (e), the first alignment film 51 'and the second alignment film 51' are formed on the transparent conductive pixel electrode formed on the glass substrate 2 which is a transparent insulating substrate. It was possible to form the alignment film 52 ′ adjacent to the above. According to a twelfth aspect of the present invention, like the sixth aspect, the first alignment film and the second alignment film are formed adjacent to each other on the transparent conductive pixel electrode formed on the transparent insulating substrate. A method for manufacturing a liquid crystal panel substrate, which is characterized in that it is characterized by forming a second alignment film utilizing water repellency. It will be described below as an eighth embodiment.

[Eighth Embodiment] In the eighth embodiment of the present invention, as shown in FIG. 9 (a), a transparent insulating substrate having pixel electrodes (not shown) is formed. The first alignment film 51 is applied on a certain glass substrate 2 to a film thickness of about 0.1 μm, and is thermally cured at 220 ° C. for about 1 hour. As the first alignment film 51, RN740 manufactured by Nissan Chemical Industries, Ltd. is selected.
After that, fluorine gas plasma 56 under reduced pressure using CF ₄ is used.
Thus, the surface of the first alignment film 51 is fluorinated by about 50 to 150Å to form a fluorinated portion 61.

Subsequently, as shown in FIG. 9B, a positive type photosensitive resin was applied to a film thickness of about 1 μm, prebaked at 100 ° C. for about 10 minutes, and selectively exposed by a photomask and ultraviolet irradiation. Then, the first alignment film 51 is developed by using the obtained predetermined photosensitive resin pattern 53 ′ as a mask.
Is etched to form 51 'as shown in FIG. 9 (c). As an etching method, it is convenient to use oxygen gas plasma including the fluorinated surface portion.

Then, as shown in FIG. 9C, after removing the photosensitive resin pattern 53 'by means such as re-irradiation with ultraviolet rays and redevelopment, as shown in FIG. When the orientation film 52 is applied to the glass substrate 2 in a thickness of about 0.1 μm, the surface of the first orientation film 51 ′ is fluorinated, so that the solvent for the second orientation film 52 and the resin concentration are Due to the high dilution, the second alignment film 52 becomes the first alignment film 51 ′.
In the above, it is water repellent and repelled so that it cannot be applied. Therefore, as shown in FIG.
The space between the patterns of 1'is filled and applied to form 52 '. Second
After the selective application of the alignment film 52 ′ of No. 2), heat treatment is performed at 170 ° C. for about 30 minutes to evaporate the diluting solvent in the second alignment film 52. As the second alignment film 52, Optomer AL3046 made by Japan Synthetic Rubber is selected.

In the final step, as shown in FIG. 9E, the first alignment film 51 'is formed by the treatment in oxygen gas plasma.
The fluorinated portion 61 on the surface of the ash is ashed to form a first alignment film 51 '.
Is exposed and a first alignment film 51 'is formed on the transparent conductive pixel electrode formed on the glass substrate 2 which is a transparent insulating substrate.
And the second alignment film 52 'could be formed adjacently. The second alignment film 5 by the treatment in oxygen gas plasma
The film thickness of 2'is also slightly reduced, but there is no problem if the coating thickness is set in anticipation of the amount.

The present invention relates to the selective coating formation of the alignment film on the pixel electrodes, and the target liquid crystal panel is not limited to the active type described in the conventional example.
It is also applicable to liquid crystal panels with simple matrix organization,
Needless to say, the present invention can be applied not only to a color display using a color filter as a counter substrate but also to a black and white liquid crystal panel, and in an active type liquid crystal display device, the switching element is not limited to the insulated gate type transistor, and the two terminals are used. It should not be necessary to explain that there is no problem even with an element.

[0065]

According to the present invention, since the unnecessary portion of the second alignment film is removed by the developer of the positive type photosensitive resin used for the selective pattern formation of the second alignment film, the number of manufacturing steps is reduced. It is possible to reduce. Further, in selectively forming the first alignment film and the second alignment film on the transparent conductive pixel electrode formed on the transparent insulating substrate, one method is to fluorinate the surface of the alignment film. Since the chemical resistance is improved by this, it is possible to avoid deterioration of the alignment film characteristics due to the decrease of the alignment film when the photosensitive resin used for the selective formation is removed. As another means, by introducing a lift-off layer, the second alignment film is selectively formed by lift-off while the first alignment film is protected by the lift-off layer, so that the alignment film is also physically and chemically damaged. Never give. Further, by other means, the second alignment film is selectively formed by utilizing the water repellency of the first alignment film whose surface is fluorinated, so that no physical or chemical damage is caused. Selective application of the alignment film is performed. As a result, it is expected that multi-domain will be realized and the viewing angle of liquid crystal panels will be expanded.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an alignment film forming process of a liquid crystal panel substrate according to a first embodiment of the present invention.

FIG. 2 is an explanatory diagram of a viewing angle widening principle according to the first embodiment of the present invention.

FIG. 3 is a cross-sectional view of an alignment film forming process of a liquid crystal panel substrate according to a second embodiment of the present invention.

FIG. 4 is a cross-sectional view of an alignment film forming step of a liquid crystal panel substrate according to a third embodiment of the present invention.

FIG. 5 is a sectional view of an alignment film forming step of a liquid crystal panel substrate according to a fourth embodiment of the present invention.

FIG. 6 is a sectional view of an alignment film forming step of a liquid crystal panel substrate according to a fifth embodiment of the present invention.

FIG. 7 is a sectional view of an alignment film forming step of a liquid crystal panel substrate according to a sixth embodiment of the present invention.

FIG. 8 is a sectional view of an alignment film forming step of a liquid crystal panel substrate according to a seventh embodiment of the present invention.

FIG. 9 is a sectional view of an alignment film forming step of a liquid crystal panel substrate according to an eighth embodiment of the present invention.

FIG. 10 is a perspective view showing a mounting means on a liquid crystal panel.

FIG. 11 is an equivalent circuit diagram of an active liquid crystal panel.

FIG. 12 is a cross-sectional view of a main part of an active type liquid crystal panel for color display.

FIG. 13 is a conceptual diagram of an alignment process for two substrates that form a liquid crystal panel.

FIG. 14 is a schematic diagram showing the molecular orientation of a TN liquid crystal panel having a conventional structure and the angle dependence of the viewing angle.

FIG. 15 is a schematic diagram showing the molecular orientation of a multi-domain TN liquid crystal panel and the angle dependence of the viewing angle.

FIG. 16 is a schematic view showing a conventional alignment treatment process for realizing a multi-domain.

[Explanation of symbols]

 2 glass substrate 9 glass substrate 51,52 alignment film 53 positive photosensitive resin 54 photomask 55 ultraviolet light 56 fluorine gas plasma 57 oxygen gas plasma 61,62 fluorinated portion of alignment film surface 63 lift-off layer 64 lift-off layer 65 negative type Photosensitive resin

Claims (12)

[Claims] 1. A first alignment film is formed on a transparent conductive pixel electrode formed on a transparent insulating substrate, and the first alignment film is partially formed on the first alignment film. Is a method for manufacturing a liquid crystal panel substrate for forming a second alignment film having a different pretilt angle, wherein the second photosensitive film is used as a developer for a positive photosensitive resin used for selective pattern formation of the second alignment film. A method for manufacturing a substrate for a liquid crystal panel, which comprises removing an unnecessary portion of the alignment film. 2. A first alignment film, the surface of which is partially fluorinated, is formed on a transparent conductive pixel electrode on a transparent insulating substrate, and the first alignment film is partially fluorinated. A liquid crystal panel substrate, wherein a second alignment film having a pretilt angle different from that of the first alignment film is formed on a fluorinated portion of the alignment film. 3. A step of forming a first alignment film on a transparent conductive pixel electrode formed on a transparent insulating substrate, a step of fluorinating the surface of the first alignment film, and Applying a second alignment film having a pretilt angle different from that of the first alignment film on the converted first alignment film, and applying a positive photosensitive resin on the second alignment film And a step of selectively exposing the inside of the pixel electrode, and developing the photosensitive resin after the exposure and selectively removing the second alignment film to expose the first alignment film. And a step of removing the photosensitive resin, and a step of removing the fluorinated surface on the first alignment film exposed by oxygen gas plasma. 4. A step of applying a first alignment film on a transparent conductive pixel electrode formed on a transparent insulating substrate; a step of fluorinating the surface of the first alignment film; Applying a second alignment film having a pretilt angle different from that of the first alignment film on the converted first alignment film; fluorinating the surface of the second alignment film; A step of applying a positive type photosensitive resin on the converted second alignment film, a step of selectively exposing the inside of the pixel electrode, and a step of developing the exposed photosensitive resin to selectively Exposing the second alignment film to the substrate, removing the fluorinated surface on the exposed second alignment film by oxygen gas plasma, and selectively removing the second alignment film. Exposing the first alignment film, removing the photosensitive resin, and using oxygen gas plasma Method of manufacturing a liquid crystal panel substrate and removing the first and second fluorinated surface on the alignment film serial exposed. 5. A first alignment film and a second alignment film having a different pretilt angle from the first alignment film are adjacent to each other on a transparent conductive pixel electrode formed on a transparent insulating substrate. A substrate for a liquid crystal panel, which is formed by: 6. A step of applying a first alignment film on a transparent conductive pixel electrode formed on a transparent insulating substrate, and a step of depositing a lift-off layer on the first alignment film. A step of selectively leaving a stacked portion including the lift-off layer and the first alignment film on the pixel electrode by using a photosensitive resin; and a second pre-tilt angle different from that of the first alignment film. Applying an alignment film, exposing the side surface of the laminated part by reducing the film thickness of the second alignment film with oxygen gas plasma, removing the lift-off layer, and removing the lift-off layer from the lift-off layer. A method of manufacturing a substrate for a liquid crystal panel, including a step of removing the second alignment film. 7. The method for producing a substrate for a liquid crystal panel according to claim 6, wherein the lift-off layer is molybdenum, and the removing liquid for the lift-off layer is hydrogen peroxide solution or dilute nitric acid. 8. The method for producing a substrate for a liquid crystal panel according to claim 6, wherein a negative type is used as the photosensitive resin, the lift-off layer is a PVA resin, and the liquid for removing the lift-off layer is water. 9. A step of applying a first alignment film on a transparent conductive pixel electrode formed on a transparent insulating substrate, and a step of depositing a lift-off layer on the first alignment film. A step of applying a photosensitive resin on the lift-off layer, and a step of selectively leaving a laminated portion composed of the photosensitive resin, the lift-off layer, and the first alignment film on the pixel electrode, A step of applying a second alignment film having a different pretilt angle from the first alignment film; a step of reducing the film thickness of the second alignment film by oxygen gas plasma to expose the side surface of the laminated portion; A method of manufacturing a substrate for a liquid crystal panel, which comprises removing the lift-off layer and removing the photosensitive resin and the second alignment film on the lift-off layer. 10. The method for manufacturing a substrate for a liquid crystal panel according to claim 9, wherein the lift-off layer is molybdenum, and the remover for the lift-off layer is hydrogen peroxide or dilute nitric acid. 11. The method for producing a substrate for a liquid crystal panel according to claim 9, wherein a negative type is used as the photosensitive resin, the lift-off layer is a PVA resin, and the liquid for removing the lift-off layer is water. 12. A step of applying a first alignment film on a transparent conductive pixel electrode formed on a transparent insulating substrate; a step of fluorinating a surface of the first alignment film; A step of selectively removing the first alignment film whose surface is fluorinated; and a step of filling a region other than the first alignment film with a second alignment film having a pretilt angle different from that of the first alignment film. And a step of removing the fluorinated surface on the first alignment film with oxygen gas plasma.