JP3105379B2 - Method for manufacturing liquid crystal electro-optical device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method of manufacturing a liquid crystal electro-optical device having a columnar resin formed by depositing and curing an uncured resin from a mixture of a liquid crystal material and an uncured resin.

[0002]

2. Description of the Related Art Recently, large-area liquid crystal displays have attracted attention. However, the enlargement of the area causes deflection of the substrate itself. For example, when a ferroelectric liquid crystal is used as a liquid crystal material, the ferroelectric liquid crystal has a layer structure, and this layer structure is deformed by deformation of the substrate. There is a problem in that the display is broken and the display is hindered, and the area cannot be increased. This problem is not limited to ferroelectric liquid crystals.
This is basically true even when another liquid crystal material is used.

In the prior art, silicon oxide spacers held between substrates have been used to maintain the spacing between the substrates.
Further, in order to eliminate bending and bulging of the substrate, an organic resin-based internal adhesive material also held between the substrates was used. The spacer literally holds the substrate interval, and the diameter of the spacer determines the substrate interval. In addition, the organic resin used for bringing the substrates into close contact with each other has a diameter larger than the required substrate spacing,
It has an effect of bringing upper and lower substrates into close contact with each other by being crushed between the substrates.

In the above-mentioned conventional structure, an orientation treatment is first performed on a substrate, then the spacer and the internal adhesive material are sprayed on one of the substrates, and then the substrates are bonded to each other. The basic manufacturing method has been to determine the interval, bond the substrates together, and then inject a liquid crystal between the substrates.

However, when the above-mentioned conventional manufacturing process was examined, it was found that when the state of the liquid crystal was changed in accordance with the alignment regulating force, the resin material for bringing the substrates into close contact with each other caused the liquid crystal to be aligned. Was found to be regulated.

[0006] The above two problems, namely: (1) A structure for keeping the substrate interval constant is required. -When aligning the liquid crystal, the material that makes the substrates adhere to each other has an adverse effect on the alignment of the liquid crystal. As a method for solving such a problem, there is an invention disclosed by the present inventors in Japanese Patent Application No. 5-55237.

According to the present invention, a mixture of a liquid crystal material and an uncured resin is provided between a pair of substrates, and an alignment means for arranging the liquid crystal material in a predetermined direction on an inner surface of at least one of the pair of substrates. The liquid crystal electro-optical device according to claim 1, further comprising a column-shaped resin formed by depositing and curing the uncured resin mixed in the liquid crystal material.

In the method of manufacturing the liquid crystal electro-optical device, a liquid crystal material is interposed between a pair of opposed substrates which have been subjected to an alignment treatment.
After mixing and encapsulating the resin material with the reaction initiator added thereto and orienting the liquid crystal, the resin component precipitated by ultraviolet irradiation or the like is cured, and the resin component is cured and formed into a column (column). Do.

The columnar resin precipitated from the liquid crystal material as described above is converted into a polymerized column spacer (Polymerized Column Spacer, P) in the sense of a columnar resin spacer.
CS).

An outline of the above configuration will be described with reference to FIG.
FIG. 1 shows an active matrix type liquid crystal display device. In FIG. 1, 101 and 102 are translucent substrates 103 and 106, pixel electrodes, 104 is a switching element, 106 is an alignment means for arranging a liquid crystal material in a certain direction, and 109 is a liquid crystal material. Liquid crystal material 1
09 is uniaxially oriented according to the orientation means 107. On the other hand, the resin 110 separated and precipitated from the liquid crystal material has a columnar (columnar) shape and is adhered to the alignment means 107 on the two substrates 101 and 102. When the alignment means is formed only on one of the substrates, the resin 110 is bonded to, for example, the alignment means 107 and the light-transmitting substrate 102 or the substrate and the electrode 103.

In order to manufacture this liquid crystal electro-optical device, the electrodes 10 whose substrate spacing is determined by the spacers 108 are used.
A mixture of a liquid crystal material and an uncured resin to which a reaction initiator has been added is sandwiched between a pair of light-transmitting substrates 101 and 102 having the light-transmitting substrates 3 and 106, and the uncured resin is mixed from the mixture between the light-transmitting substrates. By depositing the resin, the liquid crystal material is arranged along the alignment means. Thereafter, means for curing the deposited uncured resin is applied to cure the uncured resin to form a column (indicated by 110), thereby bonding the two substrates.

When the structure shown in FIG. 1 is adopted, the resin is cured after the liquid crystal material 109 is aligned according to the alignment means 107, so that a good alignment state before curing can be maintained, and the resin after curing becomes aligned. The effect is extremely small.
The column-shaped cured resin 110 has an effect of maintaining the distance between the substrates and improving the adhesion, and an effect of improving the orientation of the liquid crystal.

[0013]

2. Description of the Related Art Although the above configuration is excellent,
The position where the columnar resin is deposited cannot be controlled at all, and if the deposition positions of the liquid crystal material and the resin are biased, the uniformity of the display state is lost. Further, in a liquid crystal electro-optical device having a switching element such as a thin film transistor, if the deposition of the resin is uneven on the pixel electrode, the aperture ratio is reduced.

Further, when a ferroelectric liquid crystal is used as a liquid crystal material, the layer structure may be distorted due to the uneven deposition of the resin, and an alignment defect may occur, thereby causing a decrease in the contrast ratio.

[0015]

SUMMARY OF THE INVENTION The present invention relates to a liquid crystal electro-optical device having a columnar resin formed by depositing and curing an uncured resin from a mixture of a liquid crystal material and an uncured resin. An object is to arbitrarily control the deposition position of a cured resin.

[0016]

According to the present invention, there is provided a liquid crystal display device comprising: a mixture of a liquid crystal material and an uncured resin sandwiched between a pair of substrates; When precipitating into a shape and curing, selectively providing a hydrophobic portion and / or a hydrophilic portion on the surface of at least one of the pair of substrates in contact with the liquid crystal mixture. Thereby, the deposition position of the uncured resin is controlled.

[0017]

The present inventors have proposed a polymerization column spacer (PCS).
When preparing a liquid crystal material, the position where the uncured resin is deposited in a column from a mixture of the liquid crystal material and the uncured resin (hereinafter referred to as a liquid crystal mixture) is a hydrophobic portion of the substrate surface in contact with the liquid crystal mixture. Was found. That is, by intentionally forming a portion having hydrophobicity on the surface of the substrate in contact with the liquid crystal mixture, the resin is deposited at that portion, and it becomes possible to form a columnar resin spacer. That is, the position where the resin is deposited can be arbitrarily controlled.

As a method for making a part of the surface of the substrate hydrophobic, for example, when a screen-printing plate used for printing a sealing material that seals the peripheral portion of the substrate comes into contact with the substrate, the warp and the warp of the plate are used. There is a portion A where the weft yarn contacts and a portion B other than that, resulting in two portions A and B having different surface conditions.

At this time, the polarity of the surface tension of the surface of the substrate is changed between the portion A where the surface is pressed by the plate and the other portion. In particular, pressed parts tend to be hydrophobic.

A mixture of a liquid crystal material and an uncured resin is injected into a liquid crystal cell having two portions having different surface states as described above at a temperature indicating an isotropic phase, and gradually cooled to room temperature. First, the liquid crystal material precipitates in the above-mentioned part B when the mixture changes from the isotropic phase to the liquid crystal phase, and when further cooled, the uncured resin precipitates in the above-mentioned part A.

In addition, a coupling agent or the like is applied,
The deposition position of the column-shaped resin is specified by providing a hydrophilic or hydrophobic portion on the surface of the substrate in contact with the liquid crystal mixture by forming a film of carbon or fluorine, irradiating laser, etc. it can.

As described above, according to the present invention, it is possible to arbitrarily control the position where the columnar resin is formed, which could not be controlled conventionally. Examples will be described below.

[0023]

【Example】

FIG. 2 shows the structure of the liquid crystal cell. One substrate 111 of the liquid crystal cell was made of non-alkali glass, and an active matrix 114 using a pixel electrode 113 and a crystalline silicon TFT was formed on the substrate 111. The size of the pixel electrode was 100 μm □. The size of the matrix separated by the scanning electrodes and the signal electrodes connected to the TFT was 108 μm □. Note that an insulating film 115 was formed over the substrate. The other substrate 112 has an ITO
The film 116 was formed. An alignment film 117 was formed on the substrate on which only the electrodes were formed. The distance between the substrates was 1.5 μm.

The material of the alignment film is a polyimide resin, for example, LQ-5200 (manufactured by Hitachi Chemical), LP-64 (manufactured by Toray), RN-305 (manufactured by Nissan Chemical), etc. Here, LP-64 was used. . The orientation film was diluted with a solvent such as n-methyl-2-pyrrolidone and applied by spin coating. The coated substrate is at 250 to 300 ° C, here 28
The solvent was dried by heating at 0 ° C for 2.5 hours, and the coating film was imidized and cured. The film thickness after curing was 300 °.

Next, the alignment film is rubbed. The rubbing is 450-90 with a roller wrapped in a cloth such as rayon or cotton.
Rubbing was performed in one direction at a rotation speed of 0 rpm, here 450 rpm.

Next, as a spacer 119, a 1.5 μm-diameter true thread ball (manufactured by Kasei Kagaku Co., Ltd.) was sprayed as a spacer 119 on the substrate on which the alignment film was applied.
On the other substrate, a two-liquid epoxy adhesive is applied by screen printing as a sealant around the substrate in order to fix the two substrates, and then the two substrates are bonded. Fixed. At this time, alignment was performed so that each warp and weft of the screen plate was overlapped with the scanning electrode and the signal electrode, respectively. In the present embodiment, the mesh of the screen plate (the number of spaces surrounded by the vertical and horizontal threads per 25.4 mm) is 230, and therefore, the distance between the threads is equal to one side of the rectangular space defined by the scanning electrodes and the signal electrodes. The length is 108 μm, which is the same length, and the diameter of the yarn constituting the screen is 35 μm.

A mixture of the liquid crystal material 118 and an uncured polymer resin is injected into the cell. A biphenyl-based ferroelectric liquid crystal was used as a liquid crystal material. This liquid crystal has a phase sequence of Iso-SmA-SmC * -Cry. Structural formula _{C 8 H 17 O-C 6} H 4 -C 6 H 4 -COO-C * HCH
_{3 C 2 H 5 C 10 H} 21 O-C 6 H 4 -C 6 H 4 -COO-C * HCH
₃ C ₂ H _5, and the two materials are mixed at a ratio of 1: 1. A commercially available ultraviolet-curable resin was used as the polymer resin. The liquid crystal material and the uncured polymer resin have a weight ratio of 8
Mix at a ratio of 5:15. The mixture was stirred at a temperature that resulted in an Iso (isotropic) phase so as to mix uniformly. In the mixture, the transition point from the Iso phase to the SmA phase was lowered by 5 to 20 ° C. as compared with the case where only the liquid crystal material was used.

The above mixture was injected in a vacuum at a temperature of 100 ° C. for the liquid crystal cell and the mixture. After injection, the liquid crystal cell
It was gradually cooled at a rate of 20 ° C./hr, here 3 ° C./hr.

Observation of the orientation state of the liquid crystal cell under crossed Nicols with a polarizing microscope revealed that the extinction position at a certain rotation angle, that is, the light incident on one of the polarizing plates did not pass through the other polarizing plate, but was as if it were light. Was shut off. This indicates that the liquid crystal material has a uniform alignment (the liquid crystal molecules are aligned in one direction between the substrates).

The uncured resin is located between pixels, that is, T
It was found that the resin was deposited only on the FT and the electrode wiring portion, and little resin was deposited on the pixel electrode portion. Since the uncured resin did not show birefringence, it did not transmit light under a polarizing microscope and appeared black. In this state, the liquid crystal material and the uncured resin can be separated.

As described above, the liquid crystal material tends to precipitate in the non-pressed portion, and it was expected that the surface polarity was different between the pressed portion and the other portions. For this reason, the experiment of the change of the surface polarity by the press was simulated. In the experiment, the alignment film was pressed with a cylindrical rod, and the surface tension after that was measured. The alignment film was the same alignment film as described above, and a coating film was formed on a glass substrate under the same alignment film forming conditions and rubbing conditions. Next, the alignment film was pressed with a cylindrical rod having a diameter of 1 cm. Table 1 shows the polarity component of the surface tension of the pressure and the pressed portion at this time, and the polarity component of the surface tension of the unpressed portion.

[0033]

[Table 1]

As shown in Table 1, the value of the polar component of the pressed portion was smaller than that of the other portions. This indicates that the pressed portion is hydrophobic. At a certain pressure, especially in this experiment, 6 kgf
/ Cm ² or more tended to have no change in the magnitude of the surface tension.

In the process of forming the PCS, as described above, the liquid crystal material in the liquid crystal mixture is first oriented, and the resin material precipitates as the slow cooling proceeds. Therefore, as the process of depositing the resin on the pressed portion, the liquid crystal material is first deposited and aligned on the non-pressed hydrophilic portion of the surface, and then the resin is deposited on the pressed and hydrophobic portion. Is explained.

At this time, almost no alignment defects such as zigzag defects were found in the liquid crystal material.

Next, ultraviolet rays were irradiated to cure the polymer resin in the cell. Irradiation intensity is 3-30mW / c
m ² , here, 10 mW / cm ² , and the irradiation time is 0.1 mW / cm ² .
5 to 5 min, here 1 min.

After the ultraviolet irradiation, the alignment state of the liquid crystal cell was observed under a polarizing microscope in the same manner as described above, but the alignment state hardly changed. No effect on the orientation of the UV irradiation was observed.

The optical characteristics of the liquid crystal cell were measured. The measuring method uses a polarizing microscope using a halogen lamp as a light source, and detects the transmitted light intensity of the liquid crystal cell with a photomultiplier under crossed Nicols. Table 2 shows the results. According to the results shown in Table 2, since the cured polymer resin (hereinafter, referred to as PCS: Polymerized Column Spacer) 120 hardly exists in the electrode portion, the aperture ratio is increased and the contrast ratio is high.

[0040]

[Table 2]

The periphery of each pixel is displayed in black like a black matrix.

In the manufactured cell, the display state did not change even when the cell was made vertical. This is because the PCS scattered in the liquid crystal material adheres the two substrates to each other to keep the distance between the substrates constant, thereby preventing the cells from swelling like a gourd.

Next, the cross section of the liquid crystal cell was observed with a scanning electron microscope. The liquid crystal material was extracted with alcohol. According to the observation result, the PCS was formed in a wall shape between the two substrates except on the pixel electrodes.

The wall of the PCS was almost immediately above the signal lines and the scanning lines connecting the switching elements and the pixels, and surrounded the pixels.

In this embodiment, the case where a ferroelectric liquid crystal is used has been described. However, the structure of the present invention is not limited to the ferroelectric liquid crystal alone, and another liquid crystal material such as a nematic liquid crystal is used. It is also effective in cases. It is also effective not only in the active matrix type but also in the simple matrix type.

[0046]

According to the present invention, a resin spacer in which an uncured resin is precipitated from a mixture of a liquid crystal material and an uncured resin in a cell and cured in a column shape (polymerized column spacer = PC
In the liquid crystal electro-optical device having S), it becomes possible to deposit PCS at an arbitrary position, and the liquid crystal material and P
The positional relationship of CS became uniform over the entire liquid crystal display device, and the display state became uniform.

In addition, the occurrence of alignment defects such as zigzag defects was prevented, and the contrast ratio was improved.

In addition, it is possible to deposit resin only on portions other than the pixel electrodes. In particular, in an active matrix type liquid crystal electro-optical device in which switching elements such as thin film transistors are connected to each pixel, the switching elements other than the pixel electrodes PCS only on scanning electrodes and signal electrodes
By forming, the aperture ratio was improved, and the contrast ratio of the device was able to be improved.

When the PCS is formed above the switching element, the PCS is optically isotropic.
In the liquid crystal electro-optical device, the PCS portion is in a black state without transmitting light due to the polarizing plate. Accordingly, a role of a light-shielding film usually formed on the substrate on the counter electrode side is suppressed to suppress a change in conductivity due to light to the switching element, and the formation of the light-shielding film becomes unnecessary.

Further, a wall-shaped continuous P
Since the CS can be formed, the periphery of the pixel electrode can be displayed black as in the case of the above-described light shielding film function. Therefore, it also has an action like a black matrix particularly required in a color liquid crystal electro-optical device. The same effect is obtained when a resin is formed between the electrodes by a simple matrix type device.

[Brief description of the drawings]

FIG. 1 shows a schematic view of a liquid crystal electro-optical device containing a polymerization column spacer.

FIG. 2 is a schematic view of a liquid crystal electro-optical device according to an embodiment.

[Explanation of symbols]

 101, 111: Substrate 102, 112: Substrate 103, 113: Electrode 104, 114: Thin film transistor 105, 115: Insulating film 106, 116: Electrode 107, 117: Orientation Films 108, 118: spacers 109, 119: liquid crystal material 110, 120: polymerization column spacer

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G02F 1/1333 G02F 1/1339 500

Claims (4)

(57) [Claims] (1) A hydrophobic part and a hydrophilic part are provided.
A mixture of liquid crystal and uncured resin is provided in contact with the surface,
The cured resin is separated from the mixture, and the separated
A method for manufacturing a liquid crystal electro-optical device, comprising curing a cured resin . 2. The method according to claim 1 , wherein said surface is in contact with a surface pressed with a linear or lattice-like material.
To provide a mixture of liquid crystal and uncured resin,
Fat from the mixture, and the separated unhardened tree
A method for manufacturing a liquid crystal electro-optical device, comprising curing fat . 3. Two parts having different polar term components of surface tension.
A mixture of liquid crystal and uncured resin in contact with
The uncured resin is separated from the mixture,
A method for manufacturing a liquid crystal electro-optical device, wherein the cured uncured resin is cured. 4. The method according to claim 1, wherein the curing is performed by irradiating the uncured resin with ultraviolet rays.
A method for manufacturing a liquid crystal electro-optical device, comprising: