JP2010001482A - Liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a liquid crystal display easily and sufficiently in yield in which viscosity of a liquid crystal is suppressed low, and enhancement of a response speed, especially in halftone are attained, by using a liquid crystal material most suitable for a dropping injection method, while measuring and controlling precisely an amount of dropping of the liquid crystal by the dropping injection method. <P>SOLUTION: A sealant 21 is applied so that a starting point 31a and terminal point 31b of sealant application are located out of a frame pattern, targeting at the liquid crystal display in which the frame pattern is formed by applying the sealant 21 to a peripheral part of an image display area provided on one of a pair of substrates (substrate 22), the respective substrates are stuck together by dropping the liquid crystal into the frame pattern, and the sealant 21 is cured. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid crystal display device in which a liquid crystal is dropped into a frame pattern formed by forming an ultraviolet curable resin or an ultraviolet ray + thermosetting resin on a substrate, upper and lower substrates are bonded together, and the resin is cured.

  Conventionally, when a liquid crystal display panel is manufactured, a method of injecting liquid crystal into a panel from an injection port provided in a sealed cell is used in a liquid crystal injection process. Recently, there is a high demand for a large screen of a liquid crystal display panel, and it is becoming difficult to obtain sufficient display characteristics with this method.

Therefore, a frame pattern is formed by applying a sealing agent made of ultraviolet curable resin or (ultraviolet ray + heat) curable resin to the periphery of the image display area of the cell substrate, and liquid crystal is dropped into the frame pattern to drop each substrate. Attention has been focused on the dropping injection method of bonding the two.
This dripping injection method significantly reduces the time and simplification of the panel forming process including the liquid crystal injecting process, enables the production of a low-cost and highly reliable liquid crystal display panel, The liquid crystal display panel produced by using this method has the advantages of a very high contrast ratio from the front, excellent visual characteristics, and good black and white responsiveness. It is suitable to apply.

  As described above, the liquid crystal injection by the dropping injection method has an extremely excellent effect on the manufacturing process and the display characteristics of the product, but has various problems to be improved as described below.

-Problems with liquid crystal materials-
Currently, it is necessary to improve the display characteristics of liquid crystal display devices and at the same time lower the cost. As mentioned above, the drop injection method is effective in reducing the cost, which greatly increases the panelization process. It can be simplified. However, in the drop injection method, the method of injecting the liquid crystal material and the method of bonding a pair of substrates are significantly different from the conventional methods, so that the liquid crystal material requires a strong resistance, and a liquid crystal material suitable for the drop injection method is required. It is said that.

  In the dropping injection method, since ultraviolet rays (UV) are used for curing the sealant, a liquid crystal material having high resistance to UV is required. In addition, the liquid crystal material must be resistant to contamination of the seal, since an under-cured seal may contact the liquid crystal material.

  By the way, a liquid crystal material having a negative dielectric anisotropy is used for a vertical alignment type liquid crystal display device. In general, liquid crystal materials having a negative dielectric anisotropy are limited in the liquid crystal compounds constituting the liquid crystal materials, and those currently widely used are roughly classified into three types. By selecting and manufacturing a liquid crystal material that is as good as possible from among these liquid crystal compounds, the yield rate is increased, display unevenness, image sticking, and the like are suppressed, which contributes to a longer product life.

  One of the causes of various display irregularities and defective products is strongly related to the electrical characteristics of the liquid crystal panel, and it is necessary to increase the voltage holding ratio of the liquid crystal cell, decrease the ion density, and decrease the residual DC voltage. As the liquid crystal material, it is necessary to use a material having high purity and high specific resistance of bulk liquid crystal.

  As a result of investigating a large number of negative liquid crystals, it was found that there were some that could keep the bulk resistivity high and some that deteriorated, and that they depended on negative liquid crystal compounds. It should be noted that liquid crystal having a negative dielectric anisotropy cannot be said to use only one of the three types because of its poor material type. In order to satisfy the electro-optical characteristics as a liquid crystal display device, it is necessary to have liquid crystal properties, and it is necessary to use the above three types in combination.

  Even if the tolerance of the liquid crystal can be increased, if the viscosity of the liquid crystal increases, the response speed as a liquid crystal display device will decrease. Since the response speed is considered to be proportional to the viscosity of the liquid crystal according to the response theory of the liquid crystal, it has been desired to use a liquid crystal material having a lower viscosity.

  As explained above, the drop injection method is a technology that contributes to the efficient production of liquid crystal display panels and the realization of excellent display characteristics, but there are various problems to be improved, and there is a need for future solutions. is there.

  The present invention has been made in view of the above problems, and provides a liquid crystal display device that achieves the following objects.

  By using a liquid crystal material that is most suitable for the dropping injection method, a liquid crystal display device that realizes a further improvement in display characteristics by suppressing the viscosity of the liquid crystal and increasing the response speed, particularly halftone, is realized.

  In the liquid crystal display device and the method of manufacturing the same of the present invention, at least one of the pair of substrates is transparent, a frame pattern is formed on the periphery of the image display region by applying a sealant, and the dielectric constant is included in the frame pattern. Dropping a liquid crystal having negative anisotropy and bonding the substrates together, targeting a vertical alignment type liquid crystal display device in which the sealant is cured, including a liquid crystal compound represented by the following general formula: The liquid crystal material whose carbon number m of the terminal alkyl group is 2 or more is used.

  When a liquid crystal material containing a liquid crystal compound of the above general formula having negative dielectric anisotropy and having an even number of carbon atoms m in the terminal alkyl group is used, the specific resistance of the bulk liquid crystal can be kept high. A liquid crystal containing a neutral component having no polar group and containing an even number of m in the above general formula has an initial ratio as compared with a liquid crystal containing the same component and containing an odd number of m. In all of the resistance, the specific resistance after being left at high temperature, and the specific resistance after exposure to ultraviolet rays (UV), good results are obtained for the liquid crystal having an even number of m.

  Furthermore, among the liquid crystal compounds of the above general formula, it is desirable to use only those having an m number of 2,4. In general, when the terminal alkyl chain of the liquid crystal compound is long, the liquid crystal viscosity is increased. The liquid crystal compound of the above general formula also has an action of maintaining the nematic phase in a wide temperature range of the mixed liquid crystal even on the low temperature side. In this case, it is preferable to include two or more compounds having different m numbers. Therefore, in order to suppress the increase in the viscosity of the liquid crystal, it is preferable to use a compound having m number of 2 or 4.

  In the liquid crystal display device and the method of manufacturing the same of the present invention, at least one of the pair of substrates is transparent, a frame pattern is formed on the periphery of the image display region by applying a sealant, and the dielectric constant is included in the frame pattern. The liquid crystal material is a neutral liquid crystal compound having no polarity, intended for a vertical alignment type liquid crystal display device in which liquid crystal having negative anisotropy is dropped and the substrates are bonded together and the sealant is cured. In addition, the liquid crystal containing the neutral liquid crystal compound has high volatility in which the weight ratio decreases by 1% or more when left in a vacuum state when dropped, and has a rotational viscosity of 15 compared with the non-volatile neutral liquid crystal compound. % Or lower.

  By introducing a low-viscosity material for rotational viscosity, the viscosity of the liquid crystal can be reduced by 15% or more from the state before the introduction, and the volatility of the liquid crystal at this time is reduced by 1% or more (volatilization) by weight ratio. Show. Thus, the response speed of the liquid crystal display device can be improved by reducing the viscosity of the liquid crystal material.

  In this case, the liquid crystal material has a clearing point of 70 ° C. or higher, a dielectric anisotropy Δε of −4.0 ≦ Δε <0, and a refractive index anisotropy Δn of 0.1000 or more. It is preferable that By satisfying these conditions, display characteristics such as luminance (transmittance) and response speed and mass productivity can be improved.

  Further, it is preferable that these liquid crystal display devices have a multi-domain structure in which the liquid crystal molecules fall in two or more directions. This makes it possible to improve viewing angle characteristics, which is convenient for application to a liquid crystal monitor or the like.

  According to the present invention, by using a liquid crystal material that is most suitable for the dropping injection method, the liquid crystal viscosity can be suppressed to a low level, the response speed, particularly the halftone can be increased, and the display characteristics can be further improved. A display device can be realized.

It is a schematic sectional drawing which shows the general main structure of a liquid crystal display device. In 1st Embodiment, it is a schematic plan view which shows the mode of the glass substrate in which the frame pattern was formed before performing a liquid-crystal injection | pouring process by the dropping injection method. It is a schematic plan view which shows the main structures (2 chamfering) of the modification 1 of 1st Embodiment. It is a schematic plan view which shows the main structures (four chamfering) of the modification 1 of 1st Embodiment. It is the schematic which shows the main processes of the modification 2 of 1st Embodiment. It is a schematic perspective view which shows the board | substrate conveyance cassette of the modification 3 of 1st Embodiment. In 2nd Embodiment, after performing a liquid-crystal injection | pouring process by the dropping injection method, it is a schematic perspective view which shows the mode at the time of irradiating with an ultraviolet-ray. It is a schematic sectional drawing which expands the inside of the circle C in FIG. 7, and shows the mode of a glass substrate. It is a schematic sectional drawing which shows the comparative example of 2nd Embodiment. It is a characteristic view which shows the wavelength dependence of the transmittance | permeability. It is a characteristic view which shows the photolysis reaction of a liquid crystal. It is a schematic sectional drawing which shows the comparative examples 1 and 2 of 2nd Embodiment. It is a schematic block diagram of the liquid crystal dropping apparatus of 3rd Embodiment. It is a characteristic view which shows the output fluctuation depending on the time of an optical sensor. It is a schematic block diagram which shows the positional relationship of a dispenser and an optical sensor. It is a schematic block diagram which shows the modification 1 of the liquid crystal dropping apparatus of 3rd Embodiment. It is a schematic block diagram which shows the modification 2 of the liquid crystal dropping apparatus of 3rd Embodiment. It is a schematic block diagram which shows the modification 3 of the liquid crystal dropping apparatus of 3rd Embodiment. In 4th Embodiment, it is a characteristic view which shows the specific resistance of the initial stage of liquid crystal material, the specific resistance after high temperature leaving, and the specific resistance after ultraviolet-ray (UV) exposure. In Experimental example 1, it is a characteristic view which shows the result of having measured the voltage holding rate of each cell, the ion density, and the residual DC voltage, respectively. In Experimental example 3, it is a characteristic view which shows the result of having investigated about the volatility difference of the liquid crystal before introduce | transducing a low-viscosity material, and the liquid crystal after introduce | transducing. In Experimental example 3, it is a characteristic view which shows the result investigated about the difference in the speed-up of the liquid crystal before introduce | transducing a low-viscosity material, and the liquid crystal after introduce | transducing. It is the schematic for demonstrating the problem regarding the sealing agent in a comparative example. It is the schematic for demonstrating the problem regarding the sealing agent in a comparative example. It is the schematic for demonstrating the problem regarding the sealing agent in a comparative example.

  DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments to which the present invention is applied will be described in detail with reference to the drawings.

-General configuration of liquid crystal display-
FIG. 1 is a schematic cross-sectional view showing a general main configuration of a liquid crystal display device. The liquid crystal display device includes a pair of transparent glass substrates 1 and 2 facing each other at a predetermined interval, and a liquid crystal layer 3 sandwiched between the transparent glass substrates 1 and 2.

  A plurality of pixel electrodes 15 are formed on one transparent glass substrate 1 via an insulating layer 4, and a transparent alignment film 6 a is formed so as to cover the pixel electrodes 5. The color filter 7, the common electrode 8, and the alignment film 6b are sequentially stacked. The alignment films 6 a and 6 b are abutted so as to sandwich the liquid crystal layer 3, and the glass substrates 1 and 2 are fixed. Polarizers 9 and 10 are provided outside the substrates 1 and 2. The pixel electrode 5 is formed together with an active matrix, and in the illustrated example, a data bus line 11 of the active matrix is shown. Note that the electrode may be provided only on one of the substrates (for example, in the IPS mode).

  Here, when the liquid crystal layer 3 is formed by using the dropping injection method, examples in which various improvements are made on the structure, the manufacturing process, and the liquid crystal dropping device used for the manufacturing will be disclosed as embodiments shown below. .

  As a method of manufacturing a liquid crystal display device commonly used in each embodiment, an ultraviolet curable resin or an (ultraviolet ray + heat) curable resin is used as a main seal material, a glass substrate A serving as a TFT (thin film transistor) substrate, and a CF ( Color filter) A glass substrate B serving as a substrate is prepared. For example, a frame pattern of a main seal is formed by a dispenser on an image display area of the glass substrate B, and a liquid crystal is dropped into the frame pattern by a dropping injection method. , B are bonded together, and the main seal is cured. Thereafter, the bonded substrates A and B are cut into a TFT substrate + CF substrate state, and a liquid crystal display device is completed through various post-processes.

(First embodiment)
FIG. 2 is a schematic plan view showing a state of the glass substrate on which the frame pattern is formed before performing the liquid crystal injection process by the dropping injection method in the present embodiment. In this example, an ultraviolet resin (for example, product name 30Y-363, manufactured by ThreeBond Co., Ltd.) is used for the main seal 21, and a connecting pattern and a frame pattern are connected to the peripheral portion of the display area 23 on the glass substrate 22 side serving as a CF substrate by a dispenser. Form. The start point 31a and the end point 31b of the overlapping portion 31 are provided at positions on the non-mounting side and outside the frame pattern, and the connecting patterns are formed so as to be adjacent to each other after bonding.

  The main seal 21 has a seal width of 1 mm, and the corner portion has a radius of 1 mm so that the line width is equal to that of the straight portion. The frame pattern is formed so that the gap between the inner periphery and the light shielding film 23 is 0.5 mm after bonding.

  Next, by a liquid crystal dropping method, a required amount of liquid crystal is dropped into the frame pattern, the glass substrate 22 and the glass substrate to be the TFT substrate are bonded in a vacuum, and the liquid crystal is injected by opening to the atmosphere.

  After collectively irradiating ultraviolet rays from the glass substrate 22 side, seal hardening is performed by heat treatment, and this is cut into a predetermined dimension to obtain a liquid crystal display panel. In addition, about the cutting | disconnection of a board | substrate, the glass substrate 22 used as CF board | substrate is performed along the cutting line 32, and the glass substrate used as a TFT substrate is performed along the cutting line 33. FIG.

  Here, for comparison with the liquid crystal display device of this example, a liquid crystal display device shown in FIG. 23 is manufactured as a comparative example.

  In Comparative Example 1, a frame pattern is formed by the main seal 102 as shown in FIG. The start point and the end point are provided at positions on the frame pattern, and the frame pattern is connected at the start point and the end point (the overlapping portion 103 is formed). Otherwise, a liquid crystal display panel is obtained in the same manner as in this example.

  In Comparative Example 2, a frame pattern is formed on the main seal 102 as shown in FIG. The start point and the end point are located on the frame pattern and at a corner, and the frame pattern is connected at the start point and the end point (the overlapping portion 103 is formed). The corner portion is not formed in an arc shape. Otherwise, a liquid crystal display panel is obtained in the same manner as in this example.

  In this example, since the start point 31a and the end point 31b are outside the frame pattern, the start point 31a and the end point 31b are not overlapped on the frame pattern, and the main seal 21 of the frame pattern connecting portion does not overlap the light shielding film 23. On the other hand, in Comparative Examples 1 and 2, since the overlapping portion 103 of the start point and the end point is formed on the frame pattern, the main seal 102 of the frame pattern connecting portion overlaps the light shielding film 105. The seal width of the frame pattern connecting portions of Comparative Examples 1 and 2 is 2.6 mm, and the seal width when the main seal 102 is applied twice is 2.0 mm. This is because the dispenser moves in the vertical direction at the start point and the end point, so that the amount of seal application is larger than that of the straight line portion. The connecting portion of the frame pattern of Comparative Example 1 protrudes 0.8 mm toward the inner periphery and the gap between the inner periphery and the light shielding film 105 is 0.5 mm. Therefore, the main seal 102 overlaps the light shielding film 105 by 0.3 mm. In the frame pattern connecting portion of Conventional Example 2, the protrusion amount is the same as 0.8 mm, but the gap between the inner periphery and the light shielding film 105 is increased by 1.4 times, so the overlap between the main seal 102 and the light shielding film 105 is small. 0.1 mm. If the gap between the inner periphery and the light-shielding film is further widened, the overlap between the main seal 102 and the light-shielding film 105 can be eliminated, but this is not appropriate because the ratio of the external dimensions to the image display area is increased (widening of the frame).

  Even if the start point and the end point are formed apart on the frame pattern, the overlap between the main seal and the light shielding can be eliminated, but the seal width of the frame pattern connecting portion is narrowed and the strength required for the main seal 102 is maintained. It is not appropriate because it cannot be done.

  The liquid crystal display panels of this example and comparative examples 1 and 2 were subjected to a lighting test. As a result, display unevenness did not occur in this example, but in Comparative Examples 1 and 2, display unevenness occurred due to poor curing of the main seal 102 at the frame pattern connecting portion.

  As described above, according to the first embodiment, display unevenness due to a decrease in holding power that tends to occur due to a sealant is suppressed, and a liquid crystal display device is easily manufactured with a high yield using a dropping injection method. Thus, a highly reliable liquid crystal display device can be realized.

-Modification-
Here, various modifications of the first embodiment will be described.

(Modification 1)
In the first modification, a two-chamfered seal pattern as shown in FIG. 3 and a main seal 42 as shown in FIG. 4 are provided at the periphery of the image display area on the glass substrate 22 side serving as a CF substrate by a main seal 41 with a dispenser. A four-chamfer seal pattern is formed.

  In the two chamfering of FIG. 3, the start point 43a and the end point 43b are connected on the substrate 22 to continuously form a seal pattern as one overlapping portion 43 so that the main seal 41 does not intersect at the frame pattern connecting portion. On the other hand, in the four chamfering of FIG. 4, the start point 44 a and the end point 44 b are connected on the substrate 22 to continuously form a seal pattern as one overlapping portion 44, and the main seal 42 intersects at the frame pattern coupling portion. To do. Otherwise, the liquid crystal display panel is obtained in the same manner as in the first embodiment.

  In the two chamfering of FIG. 3, the start point 43 a and the end point 43 b are outside the frame pattern, and the main seal 41 does not intersect at the frame pattern coupling portion, so the main seal 41 at the frame pattern connecting portion does not overlap the light shielding film 23. 4, the main seal 42 intersects at the frame pattern coupling portion and the seal width becomes as thick as 2.0 mm, but is narrower than the overlapping portion 44 of the start point 44a and the end point 44b, and the coupling portion is a corner portion. Therefore, the main seal 42 at the frame pattern connecting portion does not overlap the light shielding film 23.

  Each of the liquid crystal display panels manufactured using the two chamfers of FIG. 3 and the four chamfers of FIG. 4 was subjected to a lighting test. As a result, display unevenness did not occur in both cases.

(Modification 2)
The main steps of Modification 2 are shown in FIG. Here, (a) is a schematic plan view of the substrate 22a, (b) is a schematic cross-sectional view in the vicinity of the transfer seal of the substrate 22a, and (c) is a schematic cross-sectional view showing the transfer seal in an enlarged manner.

  Here, an ITO film is formed on the surface of a resin spacer (for example, trade name Micropearl SP manufactured by Sekisui Fine Chemical Co., Ltd.) to obtain conductive particles 45. The transfer seal 24 uses the ultraviolet curable resin used in the first embodiment, and 1 wt% of the conductive particles 45 are mixed therein. When the attenuation rate of ultraviolet rays by the conductive particles 45 and the transparent electrode 46 was measured, it was found that the amount of light applied to the transfer seal 24 was 10% less than that of the main seal 21.

  Also, a reflective film 47 serving as an electrode is formed at the formation position of the transfer seal 24 on the TFT substrate side using an aluminum film. The aluminum film is formed together with the TFT film forming process. In the ultraviolet irradiation, a light amount for ultraviolet curing the main seal 21 was collectively irradiated from the substrate 22 side, and then, the transfer seal 24 was spot-irradiated with parallel light using a light guide 48 from the vertical direction of the substrate. The amount of spot irradiation was set substantially equal to the amount of attenuation of ultraviolet rays by the conductive particles 45 and the transparent electrode 46 (Modification 2A) and 2/3 of the attenuation (Modification 2B). Otherwise, the liquid crystal display panel is obtained in the same manner as in the first embodiment.

  Here, for comparison with the liquid crystal display device of this example, a liquid crystal display device shown in FIG. 24 is manufactured as a comparative example. In this comparative example, conductive particles (for example, trade name Micropearl NI manufactured by Sekisui Fine Chemical Co., Ltd.) whose surface of the resin spacer is coated with nickel are mixed into the transfer seal 106 by 1 wt%. Otherwise, a liquid crystal display panel is obtained in the same manner as in Comparative Example 1 of the first embodiment.

  The liquid crystal display panels according to the modified examples 2A and 2B and the comparative example were each subjected to a lighting test. As a result, no display unevenness occurred in the modified examples 2A and 2B, but in the comparative example, display unevenness due to poor curing occurred in the frame pattern connecting portion (overlapping portion 103) and the transfer seal 106. In Modification 2B, the amount of light applied to the transfer seal 24 is insufficient, but the reflection film 47 reflects the ultraviolet rays to compensate for the shortage, so display unevenness due to poor curing does not occur.

  If there is a slight margin between the amount of light that deteriorates the liquid crystal and the amount of light that cures the ultraviolet ray of the sealant, a reflective film is formed under the transfer seal 24 without spot irradiation on the transfer seal 24 to reduce the amount of light for batch irradiation. It is also possible to harden the transfer seal 24 with a slight increase.

(Modification 3)
In the third modification, as shown in FIG. 6, after the substrates 22 a and 22 b are bonded to each other by curing the sealing material to form the substrate 51, a transfer arm entrance / exit spacer 53 having a structure that supports the substrate 51 at multiple points is provided. The substrate transfer cassette 52 is used to perform heat treatment after the ultraviolet irradiation.

  On the other hand, as a comparative example, heat treatment after ultraviolet irradiation is performed using a substrate transport cassette 108 having a structure in which the substrate 110 is supported by the conventional substrate edge shown in FIG.

  Otherwise, the liquid crystal display panel is obtained in the same manner as in the first embodiment in both the modified example 3 and the comparative example.

  The liquid crystal display panels according to the modified example 3 and the comparative example were each subjected to a lighting test. As a result, in the third modification, no positional deviation occurred during the heat treatment, but in the comparative example, a positional deviation occurred. In Modification 3, the substrate 51 is supported at multiple points, so that the substrate 51 can be held in parallel. However, in the comparative example, since the substrate 51 is supported only at the end of the substrate, the deflection becomes large at the center of the substrate 108, and the position is during thermal curing. Deviation occurs.

  (Second Embodiment) FIG. 7 is a schematic perspective view showing a state when ultraviolet irradiation is performed after performing a liquid crystal injection step by a dropping injection method in this embodiment, and FIG. 8 shows the inside of a circle C in FIG. It is a schematic sectional drawing which expands and shows the mode of a glass substrate.

In this example, an ultraviolet curable resin (trade name 30Y-363 / manufactured by ThreeBond Co., Ltd./curing light quantity is 2500 mJ / cm ^{2 on the} I-line basis) is used for the main seal, and a CF substrate is obtained after liquid crystal is injected by a drop injection method. A glass substrate 61 and a glass substrate 62 serving as a TFT substrate are bonded together and cut out to produce a liquid crystal display panel. In this example, the ultraviolet irradiation process performed when the glass substrates 61 and 62 are bonded together is improved.

  The end of the alignment film 63 on the glass substrate 61 was formed in a region that is on the inner peripheral outer side and the outer peripheral inner side of the resin.

  For comparison, as shown in FIG. 9, a liquid crystal display panel in which an end of an alignment film 63 on a glass substrate 61 serving as a CF substrate is formed inside the inner periphery of the resin and a light shielding mask 64 is provided as a conventional example. To do.

  For ultraviolet irradiation, a high-pressure mercury lamp is used as a light source, and as shown in FIG. 7, a cut filter 64 that hardly transmits a short wavelength of less than 300 nm and a cut filter 65 that hardly transmits a long wavelength of 500 nm or more are arranged on the irradiation light source side. Do.

As shown in FIG. 10, the transmittance when both filters are combined is 50% at the 313 nm emission line peak and 90% at the 365 nm emission line peak. UV light intensity is set to 2700mJ / cm ² at I-line basis, was examined variations in the illumination area, 2300mJ / cm ² at the minimum value portion of the dispersion was 3100mJ / cm ² at the maximum value portion.

  When the transmittance of each of the glass substrate and the glass substrate to which the alignment film was added was measured, the glass substrate (trade name NA35 / NH Techno Glass Co., Ltd./0.7 mm thickness) was 84% at the 313 nm emission line peak, and the alignment film (trade name) JALS-684 / manufactured by JSR / film thickness of 80 nm) was 71%, and it was found that the wavelength was attenuated by about 15% by the alignment film.

The liquid crystal (product name: MJ961213 / Merck) is irradiated with ultraviolet rays using the long and short wavelength cut filters 64, 65, and the threshold value of the amount of ultraviolet light that activates the photolysis of the liquid crystal is obtained from the decrease in retention rate. It was. As a result, as shown in FIG. 11, the wavelength band of 313nm emission lines near the peak when irradiated with ultraviolet rays on the glass substrate over 1000 mJ / cm ² about an accumulated light quantity of (310 ± 20nm), 3000mJ / cm 2 at I-line basis The decrease in the retention rate increased with the degree, and the decrease in the retention rate was small below this. Similarly, when the threshold value of the amount of ultraviolet light that activates the photodecomposition of the liquid crystal using only the short-wavelength cut filter 64 is obtained from the decrease in the retention rate, the value is 1000 to 1500 mJ / cm on the I-line basis. ^{It was} about ² and was found to be less than half of long / short wavelength cut filters. This is because the liquid crystal is heated by irradiation with a long wavelength of 500 nm or more, and the photolysis reaction of the liquid crystal with a wavelength of 300 nm or more and less than 320 nm is promoted. Therefore, it was found that the photolysis of the liquid crystal is activated because the amount of ultraviolet light transmitted through the alignment film exceeds this value in any part of the irradiation area.

  In this example, the main seal is cured by applying the long and short wavelength cut filters 64 and 65. On the other hand, in the conventional example, only the short wavelength cut filter is applied (conventional example 1) and the long / short wavelength cut filter is applied (conventional example 2). Do. When the liquid crystal display panel thus manufactured was subjected to a lighting display inspection, in the conventional example 1, display unevenness due to a decrease in the holding ratio on the entire circumference in the vicinity of the main seal corresponds to the maximum value portion of the irradiation area in the conventional example 2. In the vicinity of the main seal, display unevenness due to a decrease in retention rate occurred. This is considered to be caused by the photolysis of the liquid crystal by ultraviolet irradiation.

  Further, in the conventional examples 1 and 2, a decrease in retention rate occurred in some corner portions. The corner portion is provided with an R (arc) so that the seal width does not become thicker when the seal is applied, so that the distance between the display area and the resin is closer than the peripheral portion. In the conventional example, since an alignment film is provided on the inner peripheral inner side of the resin, if even a little uncured component remains in the resin, it diffuses into the liquid crystal by heat treatment and reaches the limit of the display area. As a result, it is considered that a decrease in retention rate occurred in some corner portions.

  On the other hand, in this example, display unevenness due to a decrease in the retention rate that occurred in Conventional Examples 1 and 2 did not occur. This is because the photolysis of the liquid crystal is suppressed by the filter and the alignment film, and the elution of the uncured component of the resin is suppressed by the alignment film.

  As described above, according to the second embodiment, display unevenness due to a decrease in retention rate that tends to occur due to a sealing agent is suppressed, and a liquid crystal display device is easily manufactured with a high yield using a drop injection method. Thus, a highly reliable liquid crystal display device can be realized.

-Modification-
Here, a modification of the second embodiment will be described.

In this modification, the transparent electrode end and the alignment film end on the glass substrate 61 are formed in the inner and outer peripheral regions of the resin, and the liquid crystal display panel is manufactured by the same method as in the second embodiment. To do. The irradiation conditions of the ultraviolet rays are the same as those in the second embodiment except that the amount of ultraviolet rays is 3200 mJ / cm ^{2 on the} basis of the I-line. When the variation in the irradiation area was examined, the minimum value portion was 2700 mJ / cm ² and the maximum value portion was 3700 mJ / cm ² .

  When the transmittance of the glass substrate to which the transparent electrode and the alignment film were added was measured, the glass substrate was 84%, the transparent electrode (ITO / film thickness 1300A) and the alignment film were 46% at the 313 nm emission line peak, and the transparent electrode and the alignment film were aligned. It was found that the wavelength was attenuated by about 45% by the film.

  Therefore, even in the maximum value portion of the irradiation area, the amount of ultraviolet light transmitted through the transparent electrode and the alignment film is attenuated by the transparent electrode and the alignment film, so that the above threshold value is not exceeded and the photolysis of the liquid crystal is not activated. I understood.

  When the thus manufactured liquid crystal display panel was subjected to a lighting display inspection, display unevenness due to a decrease in retention rate that occurred in the conventional example did not occur. Further, since the amount of ultraviolet light irradiated to the transparent electrode and the resin outside the alignment belly end is increased, even the lowest value portion of the variation is irradiated more than the curing light amount. The strength was improved by 10%.

-Comparative examples 1 and 2-
A liquid crystal display panel is manufactured by the same method as in the second embodiment. Although the ultraviolet irradiation conditions are the same as those in the second embodiment, as shown in FIG. 12, a high-pressure mercury lamp is used as the ultraviolet irradiation light source, and a cut filter 65 that hardly transmits a short wavelength of less than 320 nm is provided on the glass substrate 61. Place on the side.

The threshold value of the amount of ultraviolet light that activates the photodecomposition of the liquid crystal using the short wavelength cut filter 65 was determined from the decrease in the retention rate, and the photodecomposition of the liquid crystal even when irradiated with 3000 mJ / cm ^{2 on the} I-line basis. Was not activated. Therefore, even if there is no filter that attenuates the wavelength of 300 nm or more and less than 320 nm, such as the transparent electrode film or alignment film in this example, in the outer peripheral inner side and outer peripheral inner side of the resin, the photolysis of the liquid crystal is not activated. I understood.

  When the liquid crystal display panel thus manufactured (Comparative Example 1) was subjected to a lighting display inspection, display unevenness due to a decrease in retention rate occurred in all stations near the main seal. When the panel was disassembled and the liquid crystal in the vicinity of the main seal was analyzed by gas chromatography, a resin component derived from the main seal was detected.

  Further, as in a known example, an ultraviolet curable resin was prepared using a photoinitiator having an absorption band on the long wavelength side of 320 nm or longer, and the same comparison was performed using this as a main seal. When the liquid crystal display panel thus prepared (Comparative Example 2) was subjected to a lighting display inspection, display unevenness due to a decrease in retention stroke occurred in a part near the main seal. When the panel was disassembled and the liquid crystal in the vicinity of the main seal was analyzed by gas chromatography, a resin component derived from the main seal was detected to a lesser extent than in Comparative Example 1.

  This is because when the resin is cured on the long wavelength side of 320 nm or more, the reaction rate of the resin is reduced by the amount of energy compared to the case where a wavelength of 300 nm or more and less than 320 nm is used. It shows that even if the absorption band of the initiator is shifted to the longer wavelength side of 320 nm or more, only the energy absorption efficiency is improved, and the reaction rate of the resin is not comparable.

(Third embodiment)
FIG. 13 is a schematic configuration diagram of the liquid crystal dropping device of the present embodiment. This liquid crystal dropping apparatus includes a dispenser 71 that discharges a predetermined amount of liquid crystal, and a measuring unit 72 that measures the amount of liquid crystal discharged by the dispenser.

  The dispenser 71 discharges a predetermined amount of liquid crystal from a needle-like discharge portion and drops it into a frame pattern formed on the glass substrate.

  The measuring means 72 includes a laser device 73 that is an irradiation light source, an optical sensor 74 that senses the laser light emitted from the laser device 73, a data logger 75 that records the output of the optical sensor 74 with respect to time, and the data And a computer 76 for analyzing and displaying the result of recording by the logger 75.

  In this liquid crystal dropping device, laser light is irradiated from the laser device 73 to the liquid crystal discharged from the dispenser 71, and the result of sensing the laser light crossing the dropped liquid crystal with the optical sensor 74 is recorded by the data logger 75. At this time, the data logger 75 records time-dependent output fluctuations as shown in FIG. 14, for example. The output of the liquid crystal is measured by integrating the output with the computer 76 over time. The computer 76 estimates the weight based on the correlation between the output of the optical sensor 74 and the weight of the liquid crystal prepared in advance.

  Although only one optical sensor is shown in the illustrated example, two optical sensors are provided to measure the amount of liquid crystal discharged from two directions that are substantially perpendicular to each other, and further provided with an optical sensor in a multifaceted manner. Even if it measures, it is suitable.

  Furthermore, the dispenser 71 discharges the liquid crystal by moving the piston in the syringe, and the control of the discharge amount is adjusted by the stroke amount of the piston, and the stroke amount of the piston is automatically set based on the result of the image processing. It is also suitable to be configured to change to

  As shown in FIG. 15, the positional relationship between the dispenser 71 and the optical sensor 74 is that about 1 cm is the most suitable because liquid droplets continuously drop from the liquid crystal discharge port to about 2 cm. It was. This is because, when the discharge distance becomes longer than 2 cm due to the pressure difference between the inside and outside of the needle or the generation of bubbles, the liquid crystal that was continuously discharged becomes discontinuous and the measurement accuracy decreases.

  The discharge amount was actually measured using this liquid crystal dropping device. At this time, the number of scans is 100,000 times per second, and the total amount of liquid crystal to be dropped is 250 mg. Since the liquid crystal is dropped at 48 locations, the drop amount per time is 5.21 mg. The dispenser 71 was set to discharge this amount.

  After dropping, the total amount dropped was estimated to be 245 mg from the output of the optical sensor 74 48 times. Therefore, 5 mg was added using a micro syringe. When the variation in the cell thickness of the liquid crystal display panel thus produced was measured, it was within a fluctuation of about 1%. In this example, since the number of times of scanning the discharged liquid crystal can be very large, even a dispenser having a function of repeating discharge in a short time can sufficiently cope with it.

  As described above, according to the liquid crystal dropping device of the third embodiment, it is possible to precisely measure and control the liquid crystal dropping amount by the dropping injection method, and appropriately adjust the dropping amount for each dropping portion. It is possible to make the cell thickness uniform and perform highly reliable liquid crystal drop injection with a high yield.

-Modification-
Here, various modifications of the third embodiment will be described.

(Modification 1)
In Modification 1, as shown in FIG. 16A, the measuring unit 77 is configured to measure the discharge amount from the liquid crystal droplet shape dropped from the dispenser 71 into the frame pattern of the glass substrate.

  The measuring means 77 calculates the area of the hatched portion of the liquid crystal 79 from the CCD 78 that images the dropped liquid crystal and the output of the CCD 78, as shown in FIG. The computer 76 is configured to estimate the weight based on the correlation with the weight (volume) of the liquid crystal.

  In the illustrated example, only one CCD is shown. However, in order to further improve the measurement accuracy, a plurality of CCDs may be provided so that the liquid crystal shape can be captured from different directions.

(Modification 2)
In the second modification, as shown in FIG. 17A, the measuring unit 81 is configured to measure the discharge amount from the shape of liquid droplets discharged from the dispenser 71 in the air.

  The measuring means 81 includes a laser device 73 that is an irradiation light source, an optical sensor 74 that senses the laser light emitted from the laser device 73, and a timing at which the optical sensor 74 recognizes the passage of liquid crystal by the laser light. As shown in FIG. 17 (b), the area of the hatched portion of the liquid crystal 79 is calculated from the CCD 78 that images the liquid crystal in the air and the output of the CCD 78, and the area and the weight of the liquid crystal ( And a computer 76 for estimating the weight based on the correlation with the volume.

  In this case, since the liquid crystal shape can be reliably captured in the air by the CCD 78, high-precision measurement can be performed without being affected by the surface shape of the glass substrate. In the illustrated example, only one CCD is shown. However, in order to further improve the measurement accuracy, it is preferable to provide a plurality of CCDs and capture the liquid crystal shape from different directions.

(Modification 3)
As shown in FIG. 18 (a), the liquid crystal dropping device of Modification 3 includes a plurality of thin glass tubes 82, and a metering dropping jig 83 which is a discharge means for discharging a predetermined amount of liquid crystal from each thin tube 82. The measuring and dropping jig 83 includes each receiving tray 84 corresponding to each thin tube 82, and includes measuring means 85 that respectively measure the weight of liquid crystal droplets received by the receiving tray 84. Liquid crystal droplets whose weight is measured by means 85 and whose discharge amount is specified are dropped and supplied into the frame pattern of the glass substrate by rotating each tray 84.

  As shown in FIG. 18B, each thin tube 82 has a structure having a highly water-repellent Teflon (registered trademark) coating on the inner surface in contact with the liquid crystal, and the liquid crystal is pushed out by an inert gas and discharged. It is said that. When the liquid crystal is dropped on the glass substrate, the liquid crystal often remains in each capillary 82, and it is preferable to promote discharge using an inert gas, and the inner surface of each capillary 82 is coated with Teflon. Thus, more effective discharge becomes possible.

(Fourth embodiment)
In this embodiment, a liquid crystal material suitable for application to a liquid crystal dropping method is disclosed. The liquid crystal material of this example includes a liquid crystal compound represented by the following general formula, and the terminal alkyl group has an even number of carbon atoms m of 2 or more.

  When a liquid crystal material containing a liquid crystal compound of the above general formula having a negative dielectric anisotropy and having an even number of carbon atoms m in the terminal alkyl group is used, the specific resistance of the bulk liquid crystal can be kept high. .

  In this example, a neutral component having no polarity is used as a common matrix, and a liquid crystal a containing an odd number of m in the general formula and an even number of m in the general formula are included. The liquid crystal a ′ was prepared, and the specific resistance values of the bulk liquid crystals were compared for the two liquid crystal materials under the following conditions.

  In all of the initial specific resistance, the specific resistance after being left at high temperature, and the specific resistance after exposure to ultraviolet rays (UV), better results were obtained when a ′ (m: even number) was used. In particular, after UV exposure, the specific resistance value can be kept high by an order of magnitude, which is very advantageous at the time of UV seal curing in the dropping injection process. These relationships are shown in FIG. Here, liquid crystal A (n = 1, 3) was used as liquid crystal a, and liquid crystal B and liquid crystal C were used as liquid crystal a ′.

  Furthermore, among the liquid crystal compounds of the above general formula, it is desirable to use only those having an m number of 2,4. In general, when the terminal of the liquid crystal compound becomes longer, the viscosity of the liquid crystal increases and the response speed decreases, which is undesirable for a liquid crystal display device. The liquid crystal compound of the above general formula also has an effect of maintaining the nematic phase in a wide temperature range of the mixed liquid crystal even on the low temperature side. In that case, the m number is preferably 2 or more. Therefore, in order to suppress the increase in the viscosity of the liquid crystal, it is desirable to use a compound having the m number of 2 or 4.

  It is also necessary to reduce the viscosity of the liquid crystal material and improve the response speed of the liquid crystal display device. In the dropping injection method, the vacuum standing state (including the exhaust time) is extremely short when bonding. Conventionally, the exhaust time which required several hours can be shortened to several minutes. For this reason, liquid crystal has been volatilized in a vacuum in the past, so it has been necessary to adjust the liquid crystal with a liquid crystal compound that suppresses its volatility, but the dripping injection method can also be used for mass production of volatile materials. became.

  In addition, when a low-viscosity material that lowers the viscosity of the liquid crystal is introduced, the viscosity of the liquid crystal can be reduced by 15% or more with respect to that before introduction (FIG. 21: liquid crystal E → liquid crystal D). It was found that the volatility of the liquid crystal at that time showed a decrease (volatilization) of 1% or more by weight.

  When the TV characteristics were measured, no significant difference was observed before and after the introduction of the low viscosity material. On the other hand, with regard to response characteristics, it was confirmed that the speed can be increased including halftones, and there is an effect.

  Also, from the relationship with the specifications of the liquid crystal display device, the clearing point of the liquid crystal material is 70 ° C. or higher, the dielectric anisotropy Δε is −4.0 ≦ Δε <0, and the refractive index anisotropy Δn is When a liquid crystal material of 0.1000 or more is used, it may mean that display characteristics such as luminance (transmittance) and response speed, and mass productivity are improved.

  Further, in this liquid crystal display device, when a multi-domain structure in which the direction in which the liquid crystal molecules fall is 2 or more, the viewing angle characteristics are excellent and convenient for a liquid crystal monitor or the like.

-Experimental example-
An experimental example in which the liquid crystal display device according to the fourth embodiment is manufactured and various display characteristics are examined will be described below.

(Experimental example 1)
Using a substrate having an ITO electrode, a brand name JALS-684 (manufactured by JSR) is formed as an alignment film by a spinner, a predetermined spacer (cell thickness: 4.0 μm) is dispersed, and a thermosetting sealant is used. Lamination and empty cells were produced.

  For these empty cells, the liquid crystal A with the m number = 1, 3 and the liquid crystals B, C with the m number = 2, 4 are injected into each empty cell, sealed, and polarized. The plate was bonded with crossed Nicols to produce a VA cell.

  As shown in FIG. 20, the voltage holding ratio, the ion density, and the residual DC voltage were measured for each cell, and the difference in electrical characteristics was examined. Liquid crystal A, liquid crystal B, and liquid crystal C have the physical property values shown in Table 1 below. Further, (a) and (b) show the voltage holding ratio, (c) shows the ion density, and (d) shows the residual DC voltage. As a result of the experiment, the electrical characteristics of liquid crystals B and C (m number = 2, 4) were improved compared to liquid crystal A (m number = 1, 3).

(Experimental example 2)
The specific resistances of the liquid crystals A, B and C were measured. Investigate against four conditions: initial value of bulk liquid crystal, after UV exposure (100 mW / cm ² , 60 seconds), after heating (120 ° C., 60 minutes), and after dropping UV curable resin (contamination dependence). It was. The liquid crystals B and C (m number = 2, 4) obtained results higher than the liquid crystal A (m number = 1, 3) under all conditions. Particularly, the data after UV exposure has a specific resistance value. It was confirmed that there was a big improvement effect that it was one digit higher.

(Experimental example 3)
The difference between the liquid crystal D before the introduction of the low-viscosity material and the liquid crystal E after the introduction was examined. The introduced liquid crystal D is a liquid crystal that does not have any problem even if the conventional vacuum dip injection is used. On the other hand, the liquid crystal E has volatility against being left in a vacuum because a low-viscosity material is introduced.

  As a result of the experiment, as shown in FIG. 21, the liquid crystal E showed a change in weight (decrease) of more than 1% when left for 1 hour, and was confirmed to be sufficiently volatile than the liquid crystal D.

  A VA cell was fabricated by the same procedure as in the third embodiment except that the spacers were changed (cell thickness: 3.5 μm) using the liquid crystals D and E. The TV characteristics are equivalent. As shown in FIG. 22, as a result of examining the response speed, the liquid crystal E in which the low-viscosity material is introduced is faster than the liquid crystal D in which the low-viscosity material is introduced with respect to all applied voltages. It was confirmed that the effect of speeding up was great in the adjustment region.

  As described above, according to the fourth embodiment, it is possible to provide a liquid crystal material most suitable for the dropping injection method, thereby suppressing the viscosity of the liquid crystal and reducing the response speed, particularly a halftone high speed. And a liquid crystal display device capable of further improving the display characteristics.

  Hereinafter, various aspects of the present invention will be collectively described as supplementary notes.

  (Appendix 1) A sealant is applied to the periphery of an image display area provided on one of a pair of substrates to form a frame pattern, and liquid crystal is dropped into the frame pattern to bond the substrates together, and the seal A method of manufacturing a liquid crystal display device by curing an agent, wherein the sealant is applied so that both a start point and an end point of the sealant application are located outside the frame pattern. Manufacturing method of display device.

  (Additional remark 2) The manufacturing method of the liquid crystal display device of Additional remark 1 characterized by applying the said sealing agent so that both the said starting point and the said end point may be located in the non-mounting side side of the said board | substrate.

  (Additional remark 3) The manufacturing method of the liquid crystal display device of Additional remark 2 characterized by connecting both the said start point and the said end point so that the said frame pattern and the said non-mounting side may be crossed.

  (Additional remark 4) The manufacturing method of the liquid crystal display device of Additional remark 1 characterized by making the said start point and the said end point correspond on the said board | substrate, and forming the sealing pattern by the said sealing agent continuously.

  (Supplementary Note 5) A sealant is applied to the periphery of an image display region provided on one of a pair of substrates to form a frame pattern, and liquid crystal is dropped into the frame pattern to bond the substrates, and the seal A method of manufacturing a liquid crystal display device by curing an agent, wherein the resin is cured on a transfer seal formed by mixing conductive particles in a resin so as to conduct between the pair of substrates. A method of manufacturing a liquid crystal display device, comprising spot-irradiating ultraviolet rays comprising: from a vertical direction or an oblique direction of a substrate.

  (Appendix 6) A sealant is applied to the periphery of an image display area provided on one of a pair of substrates to form a frame pattern, and a liquid crystal is dropped into the frame pattern to bond the substrates, and the seal A method of manufacturing a liquid crystal display device by curing an agent, and in order to conduct between the pair of substrates, a transfer seal formed by mixing conductive particles in a resin is applied, the resin is cured, and the resin is cured. A method for manufacturing a liquid crystal display device, comprising: curing a substrate by ultraviolet irradiation to bond the substrates together, and then heat-treating the substrate in a state where the substrate is held in parallel by a supporting housing after the irradiation of the ultraviolet ray. .

  (Appendix 7) A frame pattern is formed by applying a sealant around the image display area provided on one of the pair of substrates, and a liquid crystal is dropped into the frame pattern to bond the substrates together. A liquid crystal display device in which an agent is cured, wherein the pair of substrates are electrically connected by a transfer seal formed by mixing particles coated with a transparent conductive film on the surface.

  (Supplementary Note 8) A frame pattern is formed by applying a sealant around the image display area provided on one of the pair of substrates, and a liquid crystal is dropped into the frame pattern to bond the substrates together. A liquid crystal display device in which an agent is cured, wherein conductive particles are mixed in the resin, and an ultraviolet ray irradiated to cure the resin is used as an electrode under a transfer seal that conducts between the pair of substrates. A liquid crystal display device, wherein a reflective film is formed.

  (Supplementary note 9) The liquid crystal display device according to supplementary note 8, wherein an aluminum film or a silver film is used as a film reflecting ultraviolet light, and is formed on the substrate on the thin film transistor side.

  (Supplementary Note 10) A sealant is applied to the periphery of an image display area provided on one of a pair of substrates to form a frame pattern, and liquid crystal is dropped into the frame pattern to bond the substrates, and the seal A method of manufacturing a liquid crystal display device by curing an agent, wherein an alignment film of liquid crystal is formed in a region in which an end portion is an inner periphery outer side and an outer periphery inner side of the sealant, and is approximately 300 nm or more and less than 500 nm. A method of manufacturing a liquid crystal display device, wherein the sealing agent is cured by irradiating light of a wavelength.

  (Additional remark 11) At least the edge part of the alignment film on the substrate on which the color filter is formed is formed in a region which is an inner peripheral outer side and an outer peripheral inner side of the sealant, and the light of the wavelength is irradiated from the substrate side The method for manufacturing a liquid crystal display device according to appendix 10, wherein the sealing agent is cured.

  (Supplementary note 12) The liquid crystal display device according to supplementary note 10 or 11, wherein a filter that substantially cuts light other than the wavelength is disposed on the irradiation light source side as means for irradiating light having a wavelength of approximately 300 nm or more and less than 500 nm. Production method.

(Supplementary note 13) The method for manufacturing a liquid crystal display device according to any one of supplementary notes 10 to 12, wherein a curing light amount of the sealing agent is about 3000 mJ / cm ² or less in terms of I-line.

  (Supplementary Note 14) Dispensing means for discharging a predetermined amount of liquid crystal and measuring means for measuring the amount of liquid crystal discharged by the dispenser means, the measuring means having an optical sensor, and the liquid crystal discharged from the dispenser means A liquid crystal dropping device that integrates signal fluctuations of the optical sensor that occur when the optical sensor passes through the optical sensor and measures a liquid crystal ejection amount.

  (Supplementary Note 15) The measuring means scans the laser beam in a direction substantially perpendicular to the liquid crystal to be ejected, and the liquid crystal ejected traverses the laser light to change the output of the laser light and detect it by the optical sensor. 15. The liquid crystal dropping device according to appendix 14, wherein a discharge amount of the liquid crystal is measured.

  (Supplementary note 16) The liquid crystal dropping device according to supplementary note 14 or 15, wherein the measuring means measures the discharge amount of the liquid crystal from at least two directions.

  (Supplementary note 17) The liquid crystal dropping device according to supplementary note 16, wherein the measurement unit measures the discharge amount of the liquid crystal from two directions substantially orthogonal to each other.

  (Additional remark 18) The said optical sensor is installed in the position within 2 cm from the liquid-crystal discharge port of the said dispenser means, The liquid crystal dropping apparatus of any one of Additional remarks 14-17 characterized by the above-mentioned.

  (Supplementary note 19) Dispensing means for discharging a predetermined amount of liquid crystal, and liquid crystal measuring means for recognizing the shape of liquid crystal droplets discharged by the dispenser means and estimating the actual discharge amount of liquid crystal based on this. A liquid crystal dropping device.

  (Supplementary note 20) The liquid crystal dropping device according to supplementary note 19, wherein the measuring unit optically recognizes the droplet shape of the liquid crystal and estimates an actual liquid crystal discharge amount from an image of the shape.

(Supplementary Note 21) An optical sensor is provided in the vicinity of the liquid crystal discharge port of the dispenser means, and a signal of the optical sensor generated when the discharged liquid crystal passes through the optical sensor is used as a trigger signal from a liquid crystal droplet shape image. Item 20. The liquid crystal dropping device according to appendix 20, wherein an actual discharge amount of liquid crystal is estimated.

  (Appendix 22) The dispenser means discharges the liquid crystal by moving the piston in the syringe, and adjusts the control of the discharge amount by the stroke amount of the piston. Based on the result of image processing, the dispenser means The liquid crystal dropping device according to any one of appendices 19 to 21, wherein the stroke amount is automatically changed.

  (Supplementary Note 23) Liquid crystal liquid that has a plurality of thin tubes, has discharge means for discharging a predetermined amount of liquid crystal from each of the thin tubes, and has a tray corresponding to each of the narrow tubes of the discharge means, and is received by each of the trays. A liquid crystal dropping device, comprising: a measuring unit configured to measure the weight of each droplet; and supplying a liquid crystal droplet whose weight is measured by the measuring unit and whose discharge amount is specified from each of the trays.

  (Supplementary note 24) The liquid crystal dropping device according to supplementary note 23, wherein a portion of the measuring means that comes into contact with the liquid crystal is subjected to water repellent treatment to repel the liquid crystal.

(Supplementary Note 25) A pair of substrates, at least one of which is transparent, has a frame pattern formed by applying a sealant around the periphery of the image display area, and a liquid crystal having a negative dielectric anisotropy is formed in the frame pattern. A vertical alignment type liquid crystal display device in which the substrates are dropped and bonded to each other, and the sealing agent is cured, which includes a liquid crystal compound represented by the following general formula, and has a carbon number m of its terminal alkyl group A liquid crystal display device using a liquid crystal material having an even number of 2 or more.

  (Supplementary note 26) The liquid crystal display device according to supplementary note 25, wherein the liquid crystal compound has 2 or 4 carbon atoms in the terminal alkyl group.

  (Supplementary Note 27) A pair of substrates, at least one of which is transparent, has a frame pattern formed by applying a sealant around the periphery of the image display region, and a liquid crystal having a negative dielectric anisotropy is formed in the frame pattern. A vertical alignment type liquid crystal display device in which the substrates are dropped and bonded to each other, and the sealant is cured, and the liquid crystal material includes a neutral liquid crystal compound having no polarity, and a liquid crystal including the neutral liquid crystal compound Has a high volatility in which the weight ratio decreases by 1% or more when left in a vacuum when dropped, and the rotational viscosity is 15% or more lower than that of a non-volatile neutral liquid crystal compound. A liquid crystal display device.

  (Supplementary Note 28) The liquid crystal material has a clearing point of 70 ° C. or higher, a dielectric anisotropy Δε of −4.0 ≦ Δε <0, and a refractive index anisotropy Δn of 0.1000 or more. 28. The liquid crystal display device according to appendix 27, wherein

1, 2, 22 Glass substrate 21, 41, 42 Main seal 23 Light shielding film 24 Transfer seal 31, 44 Overlapping portion 31a Start point 31b End point 45 Conductive particle 46 Transparent electrode 47 Reflective film 52 Substrate transport cassette 64 Short wavelength less than 300 nm Cut filter 65 Long wavelength cut filter of 500 nm or less 71 Dispenser 72, 77, 85 Measuring means 73 Laser device 74 Optical sensor 75 Data logger 76 Computer 78 CCD
82 Thin glass tube 83 Weighing and dropping jig 84 Receptacle

Claims (4)

A pair of substrates, at least one of which is transparent, and a frame pattern formed by applying a sealant is formed in the periphery of the image display region, and a liquid crystal having a negative dielectric anisotropy is dropped into the frame pattern to A vertical alignment type liquid crystal display device in which each substrate is bonded and the sealing agent is cured,
A liquid crystal display device comprising a liquid crystal material containing a liquid crystal compound represented by the following general formula, wherein the terminal alkyl group has an even number of 2 or more carbon atoms.

  2. The liquid crystal display device according to claim 1, wherein the liquid crystal compound has a terminal alkyl group having 2 or 4 carbon atoms. A pair of substrates, at least one of which is transparent, and a frame pattern formed by applying a sealant is formed in the periphery of the image display region, and a liquid crystal having a negative dielectric anisotropy is dropped into the frame pattern to A vertical alignment type liquid crystal display device in which each substrate is bonded and the sealing agent is cured,
The liquid crystal material contains a neutral liquid crystal compound having no polarity, and the liquid crystal containing the neutral liquid crystal compound has a high volatility in which the weight ratio is reduced by 1% or more when left in a vacuum when dropped, and is non-volatile. A liquid crystal display device having a rotational viscosity of 15% or more lower than that of the neutral liquid crystal compound.   The liquid crystal material has a clearing point of 70 ° C. or higher, a dielectric anisotropy Δε of −4.0 ≦ Δε <0, and a refractive index anisotropy Δn of 0.1000 or more. The liquid crystal display device according to claim 3.

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