JP2003195320A - Liquid crystal display element and manufacturing method for laminate type liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid crystal display element which has high reliability by increasing the coupling strength between both the substrates, in a manufacturing method for a liquid crystal display element which has a liquid crystal composition held between a couple of substrates. <P>SOLUTION: In the manufacturing method for the liquid crystal display element which has a liquid crystal composition 21r, 21g, or 21b held between the couple of substrates 11 and 12 and has both the substrates connected with a seal material 24 surrounding the liquid crystal composition, unset seal materials are stuck on the substrates 11 and 12 and stuck on each other to stick both the substrates together. High polymer materials are stuck as a substrate connection base material on the substrates 11 and 12 and bonded together to stick both the substrates together. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates, and a method of manufacturing a laminated liquid crystal display device in which a plurality of such liquid crystal display devices are laminated.

[0002]

2. Description of the Related Art A liquid crystal display device basically includes a pair of substrates and a liquid crystal composition layer sandwiched between the substrates. By applying a drive voltage to the liquid crystal composition layer, the alignment of liquid crystal molecules can be controlled, and the external light input to the device can be modulated to display a desired image.

The liquid crystal composition layer is usually sealed between the substrates by a seal around the pair of substrates. The seal is usually formed by a seal wall made of a seal material sandwiched between the substrates. Both substrates are connected to each other by the sealing material.

Further, usually, spacers for disposing the space between both substrates are dispersedly arranged between both substrates. For the purpose of preventing the swelling of both substrates and maintaining a constant gap between both substrates, and improving the element strength, a substrate connection support member, that is, both substrates, is connected between the two substrates, and both substrates are connected to each other at a predetermined distance. In some cases, a support that holds the state or position may be formed. A resin structure has been proposed as such a substrate connection support.

As a method of manufacturing such a liquid crystal display element, for example, as shown in FIG. 10, an uncured sealing material SL also serving as an adhesive is applied to _one of a pair of substrates S ₁ and S ₂ (S _{1 in the} illustrated example). Then, the liquid crystal composition Lc is arranged on one end of one substrate S ₂ placed on the table BS, and one end of the other substrate S ₁ is superposed on the liquid crystal composition Lc. While sandwiching the liquid crystal composition Lc between the substrates from one end to the other end while sandwiching it with the base BS by a member R such as a roller, the both substrates are bonded together, and a seal is formed. There is a method of hardening the material. When bonding the two substrates, they are heated as needed.

In the illustrated example, a spacer for determining the inter-substrate gap is previously arranged on the substrate S ₁ and the substrate S ₂
In addition, a polymeric material such as a resin serving as a substrate connecting support for the purpose of maintaining the gap between the substrates and maintaining the overall strength is previously arranged. A liquid crystal display device can be obtained by bonding substrates in which the liquid crystal materials are arranged at the same time, and also by bonding the substrate connection support to the substrate S ₁ .

The liquid crystal display device manufacturing method described above is convenient for obtaining a liquid crystal display device having a large area because the liquid crystal composition can be surely spread and arranged between the substrates in a short time.

In addition to the above, an empty cell in which the sealing material and the substrate connecting support are sandwiched between a pair of substrates is manufactured, and a liquid crystal composition is supplied into the empty cell by a vacuum injection method or the like to form a liquid crystal display device. There is also a way to get it. In this case, at the time of manufacturing the empty cell, the sealing material is formed leaving at least a part of the liquid crystal material injection port, and the port is closed with the sealing material after the liquid crystal composition is injected.

In any case, a manufactured liquid crystal display element, for example, a red display element, a green display element and a blue display element can be laminated to obtain a full-color display type laminated liquid crystal display element. .

[0010]

However, when the substrates are bonded together with the arrangement of the liquid crystal composition between the substrates in the production of the liquid crystal display element,

(1-1) When the substrates are bonded together, the liquid crystal composition is sandwiched between the sealing material disposed on either one of the substrates and the other substrate, and the adhesive strength between the sealing material and the other substrate is high. Is reduced,

(1-2) Since the uncured state (including incompletely cured state and semi-cured state) of the sealing material and the liquid crystal composition come into contact with each other, the sealing material-containing component starts to melt into the liquid crystal display. There is a problem that display characteristics of the device may be deteriorated.

There are also the following problems. That is, in the case of providing the above-mentioned substrate connection support, usually, the polymer material M having fluidity before curing, which is the support material, is arranged on one of the substrates S in a scattered manner or the like. At that time, as shown in FIG. 11, the placed polymeric material M becomes mountain-shaped due to its fluidity and gravity, and the bottom Mb spreads over an area larger than the top Mt, while the area of the top Mt is small. turn into.

(2-1) Since the area of the bottom portion Mb is greatly expanded in this way, the aperture ratio (area ratio of the portion capable of displaying an image) in the image display portion of the final liquid crystal display element is lowered, and the bottom portion Mb is also decreased. If the amount of material to be placed is increased to compensate for the decrease in height that accompanies the expansion of the area, the bottom area will expand and the aperture ratio will decrease.

(2-2) Top M to be bonded to the other substrate
Since the area of t becomes small, the adhesive strength between the substrate connecting support and the other substrate decreases.

(2-3) When the substrates are bonded together with the interposition of the liquid crystal composition in the production of a liquid crystal display element, when the substrates are bonded, the support material disposed on one of the substrates and the other are The problem is that the liquid crystal composition is sandwiched between the substrate and the substrate, and the adhesive strength between the substrate connection support and the other substrate decreases.

Therefore, the present invention is a method of manufacturing a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates, and the bonding strength between the substrates is improved to obtain a highly reliable liquid crystal display device. It is an object to provide a method that can.
More specifically,

(1) The present invention is a method for producing a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are bonded by a sealing material surrounding the liquid crystal composition. , The bonding strength of both substrates by the sealing material is high,
It is an object of the present invention to provide a method capable of obtaining a liquid crystal display device with high reliability.

(2) According to the present invention, a liquid crystal composition in which a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are mutually connected by a substrate connecting support disposed between the pair of substrates. It is an object of the present invention to provide a method for manufacturing a display element, wherein the substrate connection support has a high adhesive strength with any substrate and a liquid crystal display element with high reliability can be obtained.

The present invention further provides a method for producing a liquid crystal display device, in which a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are bonded together by a sealing material surrounding the liquid crystal composition. Another object of the present invention is to provide a method capable of producing a liquid crystal display device by suppressing elution of a sealant component into a liquid crystal composition and obtaining a liquid crystal display device capable of displaying a high quality image.

The present invention further provides a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are connected to each other by a substrate connecting support disposed between the pair of substrates. It is also an object of the present invention to provide a method for manufacturing, which is capable of obtaining a liquid crystal display element without fear of significantly reducing the aperture ratio due to the presence of the substrate connection support. Another object of the present invention is to provide a highly reliable multilayer liquid crystal display device.

[0022]

The present invention provides the following method for manufacturing a liquid crystal display device. (1) First Method for Manufacturing Liquid Crystal Display Element A method for manufacturing a liquid crystal display element, in which a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are bonded together by a sealing material surrounding the liquid crystal composition. A first of the pair of substrates
A step of adhering the uncured seal material to the substrate, and an uncured seal material made of the same material as the second substrate of the pair of substrates to the first substrate; A substrate bonding step in which the substrates are adhered to each other and the sealing material is bonded and bonded;
At least one surface of the pair of substrates to be opposed to each other before the substrate bonding step so that the liquid crystal composition can be placed between the pair of substrates while being spread between the pair of substrates in the bonding step. Supply liquid crystal composition,
Or a liquid crystal supply step of supplying a liquid crystal composition between the pair of substrates after the substrate bonding step, wherein the adhesion of the seal material to the first and second substrates in the seal material adhesion step is performed by the first step. A method for manufacturing a liquid crystal display device, wherein the sealing material adhered to the substrate and the sealing material adhered to the second substrate are overlapped with each other in the substrate adhering step as a whole or substantially as a whole.

According to the first method of manufacturing a liquid crystal display element,
(1) An uncured sealing material for encapsulating a liquid crystal composition is attached to each of a pair of substrates for forming a liquid crystal display element. After that, the liquid crystal composition is supplied to the surface of at least one of the substrates. Further, the sealing material is adhered to each other while the supplied liquid crystal composition is spread between the substrates, and the two substrates are bonded together. Alternatively,
(2) A sealing material is attached to each of the pair of substrates for forming the liquid crystal display element. Next, the sealing materials are adhesively bonded to each other to bond the two substrates. Then, the liquid crystal composition is injected between both substrates.

As described above, the sealing material is attached to each substrate before the liquid crystal composition is supplied, and the liquid crystal composition does not enter between the sealing material and the substrate. Further, since the uncured sealing material and the substrate are in direct contact with each other, the sealing material and the substrate are strongly bonded by subsequent curing of the sealing material. Therefore, the mutual adhesive strength between the sealing material and each substrate is not weakened by the intervention of the liquid crystal composition. In addition, contact between the cured sealing material and the substrate does not cause insufficient bonding between the two.

Further, the sealing material is attached so that the sealing material attached to the first substrate and the sealing material attached to the second substrate are wholly or substantially entirely overlapped in the laminating step. When bonding substrates, first
The sealing material on the substrate and the sealing material on the second substrate entirely or substantially entirely overlap each other, and the same sealing material adheres to each other. Since the same sealing materials adhere to each other in this way, even if the liquid crystal composition may enter between the sealing materials, sufficient adhesive strength between the sealing materials can be obtained. In addition, since the sealing material attached to each substrate is made of the same material, the problem of insufficient mixing of the materials of both substrates is not caused as compared with the case where different components are attached to each substrate.

Here, "adhesion of the sealing material applied so that the sealing material applied to the first substrate and the sealing material applied to the second substrate overlap each other in the laminating step in the whole or substantially the whole" A) The adhesion of the sealing material on each substrate is arranged so as to surround the entire circumference of the liquid crystal composition arrangement area, and when they are laminated together, they are entirely overlapped with each other. B) The seal on at least one substrate Material adhesion,
The entire circumference of the liquid crystal composition arrangement region is not surrounded, and it is made in a state of being chipped at one or several places of the whole circumference. However, when both substrates are bonded, they substantially overlap each other, and by bonding the substrates, This also includes the case where the sealing material is extruded to a portion where the sealing material is lacking and adheres to the substrate. In this case, even if the liquid crystal composition may enter between the substrate and the sealing material extruded to the chipped portion, the bonding strength between both substrates may be required as a whole.

Thus, the bonding strength of both substrates is improved, and the reliability of the liquid crystal display device is improved accordingly. In addition, the bonding of the sealing materials on both substrates in the substrate bonding step is
For example, it can be done as follows. (1) If the sealing material is made of a thermoplastic resin,
The sealing materials once cooled and hardened are fused under heating and pressurization. The fused sealing material is then cured by cooling. (2) If the sealing material is made of a thermosetting resin, the sealing materials on both substrates are semi-cured in a state where the adhesiveness is left in advance, and the sealing materials are bonded together under pressure. After that, it may be further heated and cured. Alternatively, the sealing materials on both substrates are adhered to each other under heat and pressure and are semi-cured. After that, it is further heated and cured. In short, the bonding may be performed by an appropriate procedure according to the material of the sealing material.

In the first liquid crystal display device manufacturing method described above, the solubility parameter δ _LC of the liquid crystal composition and the solubility parameter δ _{R of the} sealing material are δ _R ≤ δ _LC −1 or δ _R ≧ δ _LC +
A liquid crystal composition and a sealing material satisfying the relationship of 1 in other words, 1 ≦ | δ _LC −δ _R | may be used.

By employing a liquid crystal composition and a sealing material having a solubility parameter difference of 1 or more as described above, it is possible to suppress the elution of the sealing material component into the liquid crystal composition, and to obtain a high quality liquid crystal display device. You can

(2) Second Method for Manufacturing Liquid Crystal Display Element A liquid crystal composition and a sealing material surrounding the liquid crystal composition are sandwiched between a pair of substrates, and the pair of substrates are surrounded by the seal. A method of manufacturing a liquid crystal display element in which the pair of substrates are mutually connected by a substrate connection support disposed in a region, and a step of disposing a sealing material on at least one of the pair of substrates, An uncured polymer material is attached to the first substrate of the pair of substrates as the connection support material, while an uncured polymer material is attached to the second substrate of the pair of substrates as the connection support material. A step of adhering the polymer material, a step of adhering the pair of substrates by adhering and adhering the polymer material attached thereto to the step of adhering the pair of substrates, and a step of adhering the liquid crystal composition to the pair of substrates in the step of adhering the substrate The liquid crystal composition is supplied to at least one of the surfaces of the pair of substrates that should be opposed to each other before the substrate bonding process so that the liquid crystal composition can be arranged between the substrates while being spread out to the substrate, or the substrate bonding process. A liquid crystal supplying step of supplying a liquid crystal composition between the pair of substrates later, the first and second steps in the polymer material attaching step.
The polymer material is adhered to the substrate in such a manner that the polymer material adhered to the first substrate and the polymer material adhered to the second substrate are overlapped in the bonding step. Display element manufacturing method.

According to the second method of manufacturing a liquid crystal display element, (1) an uncured polymer material (for example, a thermoplastic polymer material) is formed on each of a pair of substrates for constituting the liquid crystal display element.
Is attached. After that, the liquid crystal composition is supplied to the surface of at least one of the substrates. Further, the supplied liquid crystal composition is spread between the substrates, the polymer materials are adhesively bonded to each other, and the two substrates are bonded together. Alternatively, (2) a polymer material is attached to each of the pair of substrates for forming the liquid crystal display element. Next, the polymeric materials are adhesively bonded to each other to bond the two substrates. After that, the liquid crystal composition is injected between both substrates.

In any case, the polymer material which is the substrate connection support material is attached to each substrate before the liquid crystal composition is supplied, and the liquid crystal composition does not enter between the polymer material and the substrate. Therefore, the mutual adhesive strength between the polymer material and each substrate is not weakened by the intervention of the liquid crystal composition.

In addition, the polymer material is attached such that the polymer material attached to the first substrate and the polymer material attached to the second substrate overlap each other in the attaching step. Means that the polymeric material on the first substrate and the polymeric material on the second substrate overlap each other,
The same polymeric materials adhere to each other. Since the same polymeric materials adhere to each other in this manner, sufficient adhesive bond strength between the polymeric materials can be obtained even if the liquid crystal composition enters between the polymeric materials. .

Thus, the bonding strength between both substrates is improved by that much, and the reliability of the liquid crystal display device is improved accordingly.

Also in the second method of manufacturing a liquid crystal display element, a sealing material for sealing the liquid crystal composition between the substrates is provided. The sealing material may be provided on at least one of the substrates, and can be formed by, for example, the same method as in the first liquid crystal display element manufacturing method.

A liquid crystal composition capable of selectively reflecting visible light in a predetermined wavelength range can be mentioned as a typical example of the liquid crystal composition used in any of the above-mentioned methods for producing a liquid crystal display element. As such a liquid crystal composition, a liquid crystal composition exhibiting a cholesteric phase, such as a chiral nematic liquid crystal composition which exhibits a cholesteric phase at room temperature by adding a chiral material to nematic liquid crystal, can be exemplified.

In any of the methods for producing a liquid crystal display element according to the present invention, as a typical example of the liquid crystal composition,
Examples thereof include a chiral nematic liquid crystal composition capable of selectively reflecting visible light at room temperature.

The liquid crystal display device employing the chiral nematic liquid crystal composition can be used as a reflective liquid crystal display device capable of driving with low power consumption. In such a reflection-type liquid crystal display element, by applying a high and low pulse voltage, the liquid crystal can be switched between a planar state (colored state) and a focal conic state (transparent state) for display. Even after the application of the pulse voltage is stopped, the region in the planar state retains the planar state and the region in the focal conic state retains the focal conic state, which is so-called bistability or memory property. Thus, it is possible to keep the display even after the voltage application is stopped.

In any of the liquid crystal display element manufacturing methods according to the present invention, the following are exemplified as the liquid crystal supplying step and the substrate bonding step when the liquid crystal composition is placed between the substrates together with the substrate bonding. it can.

A) A predetermined amount of the liquid crystal composition is supplied to one or more positions on the bonding surface of one substrate of the pair of substrates to the other substrate, and the other substrate is applied from above the liquid crystal composition. Is superposed on one substrate, and the two substrates are bonded to each other while the liquid crystal composition is spread from the superposed substrate portion. In this case, if there is no problem in bonding the substrates, the liquid crystal composition is
It can be supplied to an appropriate one or two or more places such as an end portion and a central portion of the substrate surface.

B) A pair of substrates are overlapped at their one ends and are sandwiched from both sides by a sandwiching member such as a pair of pinch rollers and are passed between the members while being sandwiched between the substrates before sandwiching. The liquid crystal composition is supplied and both substrates are bonded together.

In any of the liquid crystal display elements manufactured by any of the liquid crystal display element manufacturing methods according to the present invention, a plurality of the liquid crystal display elements can be laminated to form a laminated liquid crystal display element.

For example, as one method for realizing full-color display, at least three kinds of liquid crystal layer for red display, liquid crystal layer for green display, and liquid crystal layer for blue display, each of which is sandwiched between a pair of substrates. It is possible to form a multi-layer liquid crystal display element in which the above liquid crystal layers are stacked.

[0044]

FIG. 1 is a schematic diagram showing a cross-sectional structure of a reflection type multi-layer liquid crystal display device, showing a stable state of a planar alignment of liquid crystal molecules when a high voltage pulse is applied to FIG. 1 (A). (R (red) G (green) B (blue) colored state), showing the stable state (transparent / black display state) of the focal conic alignment of liquid crystal molecules when a low voltage pulse is applied to FIG. Show. This liquid crystal display device has a memory property, and the two stable states of the planar alignment state and the focal conic alignment state of the liquid crystal molecules can be maintained even after the pulse voltage is applied.

The multi-layer liquid crystal display element shown in FIG. 1 has a red liquid crystal display element R for displaying red, a green liquid crystal display element G for displaying green, and a blue liquid crystal display element B for displaying blue.
The above three liquid crystal display elements are laminated in this order with the transparent adhesive layer N.

The liquid crystal display element (R, G, B) has a predetermined gap between the liquid crystal composition and the substrates 11 and 12 between a pair of upper and lower substrates 11 and 12 in which at least one (both here) is transparent. Gap holding material (here spacer 1)
8 and a structure 20) as a substrate connection support, and a sealing material 24 for enclosing the liquid crystal composition between the substrates. The element R is a liquid crystal composition 21r for displaying red.
The element G is a liquid crystal composition for green display 21 g, and the element B is
Holds the liquid crystal composition 21b for displaying blue.

In each of the liquid crystal display elements R, G and B of FIG. 1, the substrates 11 and 12 are transparent substrates, and are formed on the respective surfaces of the transparent substrates 11 and 12 in a plurality of parallel strips. Electrodes 13 and 14 are provided.
These electrodes 13 and 14 are opposed to each other so as to intersect each other when viewed in a direction perpendicular to the substrate. The electrodes are preferably coated with an insulating thin film.
Here, the electrodes 13 and 14 are each coated with an insulating thin film 15. Further, on the insulating thin film 15, alignment stabilizing films 16a and 16b for controlling alignment of liquid crystal molecules are provided.
Is provided.

If necessary, a visible light absorbing layer is provided on the outer surface (back surface) of the substrate opposite to the side on which light is incident. Here, the visible light absorption layer 17 is provided on the back surface of the substrate 12 in the red element R.

A pulse applying device 25 is for applying a pulsed predetermined voltage between the electrodes 13 and 14 of the liquid crystal display elements R, G and B, respectively.

The liquid crystal composition, substrate, electrodes and the like will be further described. (Liquid Crystal Composition) The Liquid Crystal Compositions 21r, 21g, 21b
Are chiral nematic liquid crystal compositions obtained by adding a predetermined amount of chiral material to the nematic liquid crystal composition,
It can selectively reflect light of a specific wavelength in visible light at room temperature.

Although not done in each liquid crystal display element shown in FIG. 1, a dye may be added to the chiral nematic liquid crystal composition. In that case, as the dye to be added, various conventionally known dyes can be used, and those having good compatibility with the liquid crystal are preferable. For example, azo compounds,
Dyes composed of quinone compounds, anthraquinone compounds, etc.,
Alternatively, a dichroic dye or the like can be used, and a plurality of types of these dyes may be used.

A color filter may be used instead of adding a dye to the chiral nematic liquid crystal composition. In this case, for example, a filter layer can be provided on the liquid crystal display element. The material used for this filter layer may be, for example, a colorless and transparent substance to which a dye is added, or a material that is essentially in a colored state without the dye being added. For example, the filter layer may be a thin film made of a specific substance that acts like a dye. Similar effects can be obtained even if the substrate itself for forming the liquid crystal display element is formed of the above filter layer material.

(Substrate) Both the substrates 11 and 12 have translucency as described above, but in an element employing only one liquid crystal material layer, the substrates 11 and 12 are at least for image observation. Therefore, a material that transmits visible light may have a light-transmitting property. A glass substrate can be given as an example of the translucent substrate. In addition to the glass substrate, a resin substrate such as polycarbonate (PC), polyether sulfone (PES), polyarylate (PAr), polyethylene terephthalate (PET) can be used. The resin substrate may be flexible.

(Electrode) The electrode is, for example, Indi
um Tin Oxide (ITO: Indium Tin Oxide), Indium Zinc Oxide (IZO:
Transparent conductive film such as indium zinc oxide), metal electrode such as aluminum and silicon, amorphous silicon, BSO (Bismuth Silicon Ox)
A photoconductive film such as ide) can be used.

In each of the liquid crystal display elements R, G and B shown in FIG. 1, a plurality of strip-shaped transparent electrodes 13 and 14 parallel to each other are formed on the surfaces of the transparent substrates 11 and 12, as described above. These electrodes 13 and 14 are opposed to each other so as to intersect each other when viewed in a direction perpendicular to the substrate.

To form the electrodes in this way, for example, an ITO film may be mask-deposited on the transparent substrate by a sputtering method or the like, or the ITO film may be formed on the entire surface and then patterned by a photolithography method.

(Insulating Thin Film) In the liquid crystal display element, an insulating thin film having a function of preventing a short circuit between electrodes or improving the reliability of the liquid crystal display element may be formed as a gas barrier layer. As described above, the insulating thin film 15 is coated on each of the electrodes 13 and 14 here.

Examples of the material of the insulating thin film include inorganic materials such as silicon oxide, titanium oxide, zirconium oxide and alkoxides thereof, and organic materials such as polyimide resin, acrylic resin and urethane resin.

The insulating thin film can be formed using these materials by a known method such as a vapor deposition method, a spin coating method or a roll coating method. Before forming the insulating thin film, the substrate surface, particularly the substrate surface on which the electrodes are formed, may be washed as necessary.

(Alignment stabilizing film) As the alignment stabilizing film,
Examples thereof include organic films such as polyimide resin, polyamideimide resin, polyetherimide resin, polyvinyl butyral resin, and acrylic resin, and inorganic films such as silicon oxide and aluminum oxide. The alignment stabilizing film formed by using these materials may be subjected to rubbing treatment or the like. Note that the alignment stabilizing film may be provided as necessary and need not be provided. The alignment stabilizing film may also serve as the insulating film.

In the multi-layer liquid crystal display device illustrated in FIG. 1, polyimide or a polyimide precursor is used as the alignment stabilizing film. Such an alignment stabilizing film can be formed, for example, as follows.

First, a polyimide or polyimide precursor obtained by polymerizing an aliphatic hydrocarbon ring tetracarboxylic acid anhydride and an aromatic diamine is used as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N- A coating solution prepared by dissolving in dimethylformamide, dimethylsulfoxide, γ-butyrolactone or the like is applied by a method such as a spin coating method or a roll coating method in the same manner as the insulating thin film. Then, it is dried in an oven or a hot plate to form an alignment stabilizing film.

The alignment stabilizing film formed by using these materials need not be subjected to rubbing treatment or the like. However, the reflectance of the device can be improved by subjecting the alignment stabilizing film on one of the pair of substrates to a weak rubbing treatment. However, in that case, the viewing angle dependency becomes large. If the alignment stabilizing films on both substrates are rubbed, the memory property in the focal conic state may be lost. The rubbing treatment may be performed in consideration of these points.

(Spacer) Between the pair of substrates of the liquid crystal display element, a spacer may be arranged for maintaining a uniform gap between the substrates. In each of the liquid crystal display elements R, G and B shown in FIG. 1, spacers 18 are scattered and arranged between the substrates 11 and 12.

Examples of this spacer include spherical spacers made of resin or inorganic oxide. Further, a fixed spacer whose surface is coated with a thermoplastic resin, for example, a silica spacer whose surface is coated with a thermoplastic resin is also preferably used. Note that, as in this example, both the spacer and the structure serving as the substrate connection support may be provided between the substrates, but instead of the structure,
It is also possible to employ only the spacer as the substrate gap holding member. When the fixing spacer is used, the fixing of the spacer to the substrate can be performed by heating the substrate to a temperature at which the spacer is fused to the substrate.

It is also possible to omit the spacer spraying step by mixing the spacer with the substrate connecting support described later, the alignment stabilizing film, or the liquid crystal composition.

(Substrate connection support) The liquid crystal display element has a strong self-coupling property such that a pair of substrates are firmly bonded to each other to prevent the substrates from bulging and the substrate gap is maintained at a predetermined value against a pressing force. It is desirable to have retention properties. Therefore, in order to impart such self-holding property, a substrate connecting support for connecting the two substrates to each other can be provided between the pair of substrates. Each of the liquid crystal display elements R, G, and B of this example has a structure 2 between the substrates 11 and 12 as such a substrate connecting support.
0 is provided.

Explaining the structure surface of such a structure, the structure is, for example, a columnar body, a quadrangular columnar body, an elliptic cylinder, which are arranged in a dot pattern in a predetermined pattern such as a lattice array at regular intervals. Examples thereof include columnar structures such as a body, a trapezoidal columnar body, and a conical columnar body. Further, it may be stripe-shaped ones arranged at predetermined intervals. The columnar structure is not a random array, but an array of even intervals, an array in which the intervals gradually change, an array in which a predetermined layout pattern is repeated at a constant cycle, and the like, can properly maintain the space between the substrates, and display an image. It is preferable that the arrangement is such that it does not interfere with The arrangement of the columnar structures is such that the ratio of the area occupied by the display region of the liquid crystal display element is about 1% to 40% (in other words, in order to obtain characteristics that are practically satisfactory as a liquid crystal display element while maintaining an appropriate strength. The area ratio of the displayable portion in the display area, that is, the aperture ratio is 99% to 60%
Is preferred.

Next, the materials will be described. As the material of the columnar structure, the same material as the sealing material described later can be adopted. For example, it can be formed using a polymer material. As the polymer material, any general polymer material can be used, and various thermoplastic polymer materials, thermosetting polymer materials, and photocurable polymer materials can be used.

As the thermoplastic polymer material, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polymethacrylate ester resin, polyacrylate ester resin, polystyrene resin, polyamide resin, polyethylene resin, polypropylene resin, Examples thereof include fluorine resin, polyurethane resin, polyacrylonitrile resin, polyvinyl ether resin, polyvinyl ketone resin, polyether resin, polyvinylpyrrolidone resin, saturated polyester resin, polycarbonate resin, and chlorinated polyether resin.

Examples of the thermosetting polymer material include epoxy resin, phenol resin, polyester resin, polyimide resin, polyamideimide resin and silicone resin.

Examples of the photocurable polymer material include photocurable resins such as acrylic resins and methacrylic resins.

Further, a material containing a volatile solvent may be used as the material for the substrate connecting support. As such a volatile solvent, an aromatic solvent, an aliphatic solvent, an ether solvent, a halogenated hydrocarbon solvent, an ester solvent, a ketone solvent, etc., which are uniformly mixed with the resin material, Any material that volatilizes within the range of room temperature to the heat resistant temperature of the substrate may be used.

Specific examples thereof include xylene, toluene, hexane, diethyl ether, dipropylene glycol methyl ether, butyl acetate, methyl ethyl ketone, methyl carbitol, dimethylformamide (DMF) and dimethyl adipate.

By containing a volatile solvent, the material resin can be made into a paste with a desired viscosity. Further, for example, when a thermoplastic polymer material is used as the material resin, after forming the substrate connection support body, It can be solidified by drying, which can reduce the change in shape of the substrate connection support when the two substrates are superposed.

Regarding the adhesion of the substrate connection support material to the substrate, a resin material such as a printing method in which a resin material is extruded by using a screen plate or a metal mask, a dispenser method, an ink jet method or the like is formed by ejecting from a nozzle tip. Method, after supplying the resin material on the flat plate or roller,
This can be done by a method such as transferring onto the substrate surface.

The substrate connection support in each liquid crystal display device is formed on one of the substrates prior to the liquid crystal composition supplying process and the substrate bonding process for manufacturing the device, and this is formed in the substrate bonding process. It can also be adhered to the other substrate.

However, as described above, for example, when the fluid resin before curing, which is the substrate connecting support material, is arranged on one of the substrates in a dotted manner, as shown in FIG. The placed material M becomes a chevron, and the bottom Mb
Is spread over a larger area than the top Mt, while the area of the top Mt is reduced.

Since the area of the bottom portion Mb is greatly expanded in this way, the aperture ratio (area ratio of the area where an image can be displayed) in the image display portion of the final liquid crystal display element is reduced, and the bottom area is expanded. If the amount of resin to be arranged is increased to compensate for the decrease in height, the area of the bottom portion becomes wider and the aperture ratio decreases.

Also, the top M to be adhered to the other substrate
Since the area of t becomes small, the adhesive strength between the substrate connection support and the other substrate decreases.

Furthermore, when the liquid crystal composition is sandwiched between the support material disposed on one of the substrates and the other substrate at the time of bonding the substrates, the substrate connection support and the other substrate are adhered to each other. Strength is reduced.

Therefore, when providing the substrate connection support, for example, one substrate 1 of the pair of substrates 11 and 12 is used.
1 (or 12) is adhered with an uncured polymer material (for example, a thermoplastic polymer material) which is not yet cured, in other words, which exhibits fluidity, while being cured on the other substrate 12 (or 11). The previous polymer material (for example, the same thermoplastic polymer material) is attached, and then the liquid crystal composition 21r or 21g or 21b is supplied to at least one of the surfaces of the pair of substrates to be opposed to each other, and then the liquid crystal composition 21r or 21g or 21b is supplied. The liquid crystal composition thus obtained is spread between the substrates 11 and 12, and the polymer material attached to the substrates can be adhered and bonded to each other. The uncured polymer material placed on both substrates is
From the viewpoint of maximizing the adhesive strength between the two substrates, it is preferable to provide the same size and the same shape at positions on the respective substrates which overlap each other when the two substrates are superposed.
From the viewpoint of facilitating the device production, the shapes, sizes, and positions may be slightly shifted as long as the polymer materials of both substrates are overlapped to the extent that sufficient adhesive strength is obtained.

The liquid crystal composition may be supplied into the empty cell after forming an empty cell in which both substrates are bonded together. When a thermoplastic polymer material is used as the substrate connection support material, the polymer materials on both substrates can be easily bonded to each other by heating and fusing them together.

In any case, the substrate connection support material is attached to the substrates 11 and 12 so that the material attached to one substrate and the material attached to the other substrate overlap in the substrate bonding step. To do.

By doing so, the substrate connection support material is attached to each substrate before the liquid crystal composition is supplied, and the liquid crystal composition does not enter between the material and the substrate. Therefore, the mutual adhesive strength between the material and each substrate is not weakened by the intervention of the liquid crystal composition.

Further, the substrate connection support material is attached such that the material attached to the substrate 11 and the material attached to the substrate 12 overlap each other in the substrate attaching step. , The material on the substrate 11 and the material on the substrate 12 overlap with each other, and the same material adheres to each other. Since the same materials adhere to each other in this way, even if the liquid crystal composition may enter between the materials, sufficient adhesion strength between the materials can be obtained.

In addition, the height of the support material on each substrate can be lowered by distributing and attaching the substrate connection support material to both substrates in this way, and the area of the bottom of the adhered material can be reduced by the material and the substrate. It is possible to reduce the size while ensuring sufficient adhesive strength with, and to reduce the area of the material bottom in this way, so that the outer diameter of the substrate connection support formed between both substrates by bonding the materials on both substrates is that much. The size of the liquid crystal display device can be reduced, and the aperture ratio of the liquid crystal display device can be improved.

Thus, the bonding strength of both substrates is improved by that much, and the reliability of the liquid crystal display device is improved accordingly. Also,
The aperture ratio is also improved.

When the substrate connecting support material is attached to each substrate as described above, the height of the support material attached to each substrate is determined by the thickness of the desired liquid crystal composition layer, in other words, between the desired substrates. Must be 1/2 or more of the gap.

When the two substrates are bonded together, the height of the opposing substrate connecting support materials is set to be larger than the desired substrate gap so that the opposing support materials exhibit mutual adhesiveness. it can. The height of the substrate connection support material attached to each substrate is preferably 5 times or less, more preferably 2 times or less, the thickness of the desired liquid crystal composition layer. By making the thickness of the desired liquid crystal composition layer to be twice or less, it is possible to minimize the displacement, breakage, or expansion of the substrate connection support when the substrates 11 and 12 are superposed. it can.

When a thermoplastic polymer material is used as the substrate connection support material, the substrate bonding step is performed under heating to fuse the polymer materials on both substrates with each other. When the substrates are superposed on each other, this may be carried out at room temperature, or may be carried out by heating them to a temperature not lower than the softening temperature of the thermoplastic polymer material on each substrate. When stacking at room temperature, it is possible to suppress positional displacement and distortion during bonding due to heat shrinkage of the substrate and other constituent materials. When the support materials are heated to a temperature above the softening temperature and superposed, the support materials on both substrates can be fused with each other with less trouble.

In any case, the substrates are bonded to each other by applying pressure to both the substrates while heating them above the softening temperature of the support materials, whereby the opposing support materials on both the substrates are fused to each other. Thus, the height of the fusion bonded support material can be made equal to the inter-substrate gap defined by the particle size of the spacer. After fusion, it can be solidified by cooling.

The size of the substrate connecting support material to be attached to each substrate is such that the maximum diameter is 20 when it is attached in a dot shape.
The size of 0 μm or less is desirable in consideration of adhesiveness and device display characteristics, and the size of maximum diameter is preferably 10 μm or more in consideration of ease of production and adhesiveness.

(Sealing Material) As the sealing material 24 in each of the liquid crystal display elements R, G, B, the same material as the material for supporting the substrate can be adopted. For example, an epoxy resin, a silicone resin, a polyurethane resin, an acrylic resin, or the like, or a thermosetting resin, a photocurable resin, or a thermoplastic resin containing a precursor thereof as a main component can be used.

These resins can be attached to the substrate by a method such as a screen printing method or a dispenser method. The sealing material resin attached to the substrate can be heated for temporary curing or drying depending on the type of resin, and then used for bonding the substrates and finally for curing (main curing). Processing etc. can be given.

The sealing material in each liquid crystal display element is formed on one of the substrates prior to the liquid crystal composition supplying step and the substrate bonding step for manufacturing the element, and this is applied to the other substrate in the substrate bonding step. It can also be adhered to a substrate.

However, when the substrate bonding accompanied by the filling of the liquid crystal composition is adopted in the production of the liquid crystal display element, as described above, it is arranged on one of the substrates 11 (or 12) at the time of the substrate bonding. The liquid crystal composition 21r or 21g or 21b is sandwiched between the sealing material 24 and the other substrate 12 (or 11), and the adhesive strength between the sealing material 24 and the other substrate 12 (or 11) is reduced.

Therefore, when providing the sealing material,
For example, one of the pair of substrates 11 and 12 is the substrate 11
While the uncured sealing material is attached to (12), the uncured sealing material is also attached to the other substrate 12 (11), and then the liquid crystal composition is applied to at least one of the surfaces of the substrates 11 and 12 that should face each other. Object 21r or 21g or 21b is supplied, and then the supplied liquid crystal composition is spread between the substrates 11 and 12, and the substrates are adhered to each other and the sealing materials are adhered to each other, and the sealing material is cured. Can be made.

In this case, the sticking of the sealing material to the substrates 11 and 12 may be carried out by the sealing material attached to one of the substrates 11 and the sealing material attached to the other of the substrates 12 as a whole or in the substrate bonding step. It is done so that it is almost entirely overlapped.

In this way, the sealing material is attached to each substrate before the liquid crystal composition is supplied, and the liquid crystal composition does not enter between the sealing material and the substrate. Therefore, the mutual adhesive strength between the sealing material and each substrate is not weakened by the intervention of the liquid crystal composition.

Further, the sealing material is adhered so that the sealing material adhered to the substrate 11 and the sealing material adhered to the substrate 12 are entirely or substantially entirely overlapped with each other in the laminating step. In the matching, the sealing material on the substrate 11 and the sealing material on the substrate 12 are entirely or substantially entirely overlapped with each other, and the same sealing materials are adhered to each other. Since the same sealing materials adhere to each other in this way, even if the liquid crystal composition may enter between the sealing materials, sufficient adhesive bonding strength between the sealing materials can be obtained.

Thus, the bonding strength between both substrates is improved, and the reliability of the liquid crystal display device is improved accordingly. In addition, from the viewpoint of maximizing the adhesive strength between both substrates, the pre-curing sealing material to be placed on both substrates is provided in the same size and the same shape at the positions on the respective substrates which overlap each other when the both substrates are superposed. It is preferable. However, if sufficient adhesive strength of the substrate is obtained and the sealing of the liquid crystal composition is sufficient, the adhesion of the sealing material on at least one substrate is
It is not designed to surround the entire liquid crystal composition placement area,
It is made in a state where it is chipped at one or several points of the entire circumference, but when both substrates are bonded, they overlap each other almost entirely, and the bonding of the substrates causes the sealing material to be extruded to the part where the sealing material is missing. It is also possible to adopt a mode of adhering to the substrate. Also, from the viewpoint of facilitating device manufacturing, the shape, size, and position may be slightly shifted within a range in which sufficient adhesive strength of the substrate is obtained and liquid crystal sealing is not impaired.

In the production of each liquid crystal display element, the liquid crystal composition 21r (or 21g or 21b) and the sealing material 24 are used.
As the solubility parameter δ _LC of the liquid crystal composition and the solubility parameter δ _R of the sealing material, a relation of δ _R ≦ δ _LC −1 or δ _R ≧ δ _LC +1, in other words, 1 ≦ | δ _LC −δ _R ｜
It is desirable to use a liquid crystal composition and a sealing material that satisfy the relationship of.

By employing a liquid crystal composition and a sealing material having a solubility parameter difference of 1 or more as described above, the elution of the sealing material component into the liquid crystal composition can be suppressed, and a high quality liquid crystal display device can be obtained. You can

Next, some examples of a method for manufacturing a liquid crystal display device by attaching a sealing material to each of a pair of substrates while considering the solubility parameter (SP value) of the sealing material and the liquid crystal composition (Examples) 1 to 7), comparative examples (Comparative Examples 1 and 2) are also described, and evaluation results thereof are also described. The present invention is not limited to these examples.

The reflectance of the produced liquid crystal display element was measured by measuring the luminous reflectance (Y value) using a spectrocolorimeter CM-3700d (manufactured by Minolta). The smaller the Y value, the more transparent. The contrast is given by (Y value in high reflectance state / Y value in low reflectance state). In the liquid crystal display element in each of the examples described below, the liquid crystal display element is in a high reflectance state when it is in a planar state (colored state), and is low when it is in a focal conic state (transparent state / black display). It becomes a reflectance state.

The solubility parameter (SP value) of the liquid crystal composition and the sealing material was determined as follows. The liquid crystal composition is dissolved in an organic solvent such as n-hexane, cyclohexane, methyl isobutyl ketone, ethyl acetate, dioxane, isopropyl alcohol, and methyl alcohol, and the SP value of the most soluble organic solvent is the SP of the liquid crystal composition.
Value. The SP value was similarly determined for the sealing material.

According to JIS, the adhesive strength of the sealing material is measured.
A 180 ° peel test was performed according to the method described in K6854-9. Each of the liquid crystal display elements described below,
The liquid crystal composition shown in FIG. 10 was placed between the substrates, and the two substrates were bonded to each other.

(Example 1) Refractive index anisotropy Δn: 0.15
2, dielectric anisotropy Δε: 7, isotropic phase transition temperature T _NI : 90
31.degree. C. of the nematic liquid crystal mixture A to 68.5 parts by weight of chiral material (S-811 manufactured by Merck & Co., Inc.).
5 parts by weight was added to prepare a chiral nematic liquid crystal composition al that selectively reflects light having a wavelength near 560 nm. The SP value of the liquid crystal composition al was measured and found to be about 9.

First, a coating solution of an insulating film material containing an organosilicon compound containing titanium oxide fine particles was applied by flexographic printing on an ITO transparent electrode provided on a first polycarbonate (PC) film substrate. Then, the coating solution is heated in an oven at 80 ° C. to remove the solvent and dried, and then UV irradiation (3 J / cm ² ) is performed with a high pressure mercury lamp.
And then baked in an oven at 140 ° C for 1 hour to obtain a thickness of 2
An insulating film of 00 nm was obtained.

A coating solution of soluble polyimide was applied onto the insulating film by flexographic printing. Then, it was baked in an open at 140 ° C. to obtain a polyimide-based alignment stabilizing film having a thickness of 50 nm. Then, a 6 μm-diameter fixed spacer formed by coating a thermoplastic resin was sprinkled and attached thereon.

In addition, ITO on the second PC film substrate
Similarly, an insulating film and an alignment stabilizing film are formed on the transparent electrode,
The opposite substrate was used.

Then, as shown in FIG. 2, a polyurethane resin (SP value 8 manufactured by Dainippon Ink and Chemicals, Inc.) and dimethylformamide were used as a sealant at a weight ratio of 5 at the peripheral portion of the first substrate surface.
A mixture of 0:50 was applied in an annular shape by screen printing to form a wall having a height of 5 μm.

Next, a mixture of the polyurethane resin and dimethylformamide is applied by screen printing to the peripheral portion of the surface of the second substrate and the image display area portion to correspond to the seal material wall pattern on the first substrate. An annular sealing material wall is formed with a height of 5 μm, and a columnar structure having a substantially columnar shape is formed with a height of 1 μm, as schematically shown in FIG.
It was formed in a dot-like lattice array with 0 μm and pitch pt = 300 μm.

After that, the first and second substrates are subjected to 1 ° C. at 140 ° C.
Heated and dried for hours. After that, after applying the liquid crystal composition al in an amount calculated from the height of the inter-substrate sealing material to be finally formed on the second substrate and the area of the inner region thereof, the first substrate is pressed. Then, the liquid crystal cell (liquid crystal display element) Cl was produced by bonding the liquid crystal cell to the second substrate while heating.
Furthermore, a black light absorbing layer was provided on the outer surface of the substrate on the side opposite to the side on which light was incident (image observation side).

A predetermined pulse voltage was applied to bring the liquid crystal cell Cl into a colored state and a decolored state. The pulse voltage applied for coloring / decoloring at this time has a pulse width of 5 msec.
The voltage value was 32V / 15V. Further, the Y value during color display was 25.6, the Y value during black display was 1.6, and the contrast was 16: 1, and the device was a device having high contrast with good color / black display characteristics.

In order to investigate the shape retention of the cell and the solubility of the sealing material in the liquid crystal composition, the liquid crystal cell Cl was heated at 80 ° C. for 25 hours, and the display characteristics were measured. It was confirmed to be a highly reliable element.

The adhesive strength of the sealing material portion of the liquid crystal cell Cl was measured by a 180 ° peel test to find that it was 6 gf / m.
m, and the strength was sufficient to maintain the cell gap (inter-substrate gap).

Example 2 A liquid crystal composition al (SP value of about 9) was prepared in the same manner as in Example 1, and the first and second P
An insulating film and an alignment stabilizing film were formed on the C substrate. And
The same fixed spacers having a diameter of 6 μm as in Example 1 were scattered and attached on the first substrate.

Then, a silicone adhesive (Toray Dow Corning Silicone,
SP value 7.5) is applied in a ring shape by screen printing,
A wall with a height of 5 μm was formed.

Next, a mixture of polyurethane resin (SP value 8 manufactured by Dainippon Ink and Chemicals, Inc.) and dimethylformamide in a weight ratio of 50:50 was applied to the display portion on the second substrate in a dot shape by screen printing, After drying at 140 ° C. for 1 hour, a columnar structure having a height of 10 μm and a diameter of 50 μm and having a substantially columnar shape was formed in a grid-like arrangement with a pitch of 300 μm.

Further, the silicone adhesive was screen-printed on the second substrate so as to correspond to the sealing material wall pattern on the first substrate, and a sealing material wall having a height of 5 μm was formed. .

Then, after applying the liquid crystal composition al on the second substrate in an amount calculated from the height of the final sealing material and the area inside the final sealing material, the second substrate is pressurized and heated to the second substrate.
It was attached to a substrate and heated at 150 ° C. for 1 hour to prepare a liquid crystal cell (liquid crystal display element) C2. Furthermore, a black light absorbing layer was provided on the outer surface of the substrate opposite to the side on which light was incident.

A predetermined pulse voltage was applied to bring the liquid crystal cell C2 into a colored state and a decolored state. The pulse voltage applied for coloring / decoloring at this time has a pulse width of 5 msec.
The voltage value was 33V / 16V. Further, the Y value during color display was 28.0, the Y value during black display was 1.6, and the contrast was 17.5: 1, and the device was a device having a high contrast in both color and black display characteristics.

After the liquid crystal cell C2 was heated at 70 ° C. for 25 hours and the display characteristics were measured, there was no change from that before heating, and it was confirmed that the device had high reliability.

Further, the adhesive strength of the sealing material portion of the liquid crystal cell C2 was measured by the 180 ° peel test, and it was 10.9 g.
f / mm, which was a sufficient strength to maintain the cell gap.

Example 3 A liquid crystal composition al (SP value: about 9) was prepared in the same manner as in Example 1, and the first and second P
An insulating film and an alignment stabilizing film were formed on the C substrate. And
On the first substrate, the same fixed spacers having a diameter of 6 μm as described above were scattered and attached.

Subsequently, an epoxy adhesive (manufactured by Mitsui Chemicals, SP value 10) was circularly applied to the peripheral portion of the surface of the first substrate by screen printing, and then heated and dried at 80 ° C. for 30 minutes,
A wall with a height of 5 μm was formed.

Next, a mixture of polyurethane resin (SP value 8 manufactured by Dainippon Ink and Chemicals, Inc.) and dimethylformamide in a weight ratio of 50:50 was applied to the display portion on the second substrate in a dot form by screen printing, After drying at 140 ° C. for 1 hour, a columnar structure having a height of 10 μm and a diameter of 50 μm and having a substantially columnar shape was formed in a grid-like arrangement with a pitch of 300 μm.

Further, the epoxy adhesive was applied in a ring shape by screen printing on the second substrate so as to correspond to the seal material wall pattern on the first substrate, and the epoxy adhesive was heated and dried at 80 ° C. for 30 minutes to obtain a high temperature. A 5 μm thick sealing material wall was formed.

Then, after applying the liquid crystal composition al on the second substrate in an amount calculated from the height of the final sealing material and the area inside thereof, the second substrate is pressurized and heated to the second substrate.
It was attached to a substrate and heated at 150 ° C. for 1 hour to prepare a liquid crystal cell (liquid crystal display element) C3. Furthermore, a black light absorbing layer was provided on the outer surface of the substrate opposite to the side on which light was incident.

A predetermined pulse voltage was applied to bring the liquid crystal cell C3 into a colored state and a decolored state. The pulse voltage applied for coloring / decoloring at this time has a pulse width of 5 msec.
The voltage value was 31V / 16V. In addition, the Y value during color display was 28.6, the Y value during black display was 1.8, and the contrast was 15.9: 1, and the device was a device with good contrast in both color and black display characteristics.

After the liquid crystal cell C3 was heated at 70 ° C. for 25 hours and the display characteristics were measured, there was no change from that before heating, and it was confirmed that the device had high reliability.

The adhesive strength of the sealing material portion of the liquid crystal cell C3 was measured by a 180 ° peel test to find that it was 10.1 g.
f / mm, which was a sufficient strength to maintain the cell gap.

(Example 4) 6 of nematic liquid crystal mixture A
With respect to 7.7 parts by weight, 3.3 parts by weight of chiral material S-811 (manufactured by Merck & Co.) and MLC-624 of chiral material are used.
7 (manufactured by Merck & Co., Inc.) was added in an amount of 29 parts by weight to prepare a liquid crystal composition dl which selectively reflects light having a wavelength near 680 nm.

Further, with respect to 64.6 parts by weight of the nematic liquid crystal mixture B having a refractive index anisotropy Δn: 0.182, a dielectric anisotropy Δε: 10 and an isotropic transition temperature T _NI : 95 ° C. 2.9 parts by weight of material S-811 (made by Merck) and 32.5 parts of chiral material MLC-6247 (made by Merck).
By adding parts by weight, a liquid crystal composition d2 that selectively reflects light having a wavelength near 560 nm was prepared.

With respect to 62 parts by weight of the nematic liquid crystal mixture B, 3.0 parts by weight of the chiral material S-811 (manufactured by Merck) and 35.0 parts by weight of the chiral material MLC-6247 (manufactured by Merck). A liquid crystal composition d3 which was added to selectively reflect light having a wavelength near 480 nm was prepared.

The SP values of the liquid crystal compositions dl, d2 and d3 were measured and found to be about 9.

Then, similarly to the first embodiment, an insulating film and an alignment stabilizing film were formed on the first and second polycarbonate (PC) substrates.

Then, an epoxy adhesive similar to that used in Example 3 (manufactured by Mitsui Chemicals, SP value 1) was applied to the peripheral portion of the first substrate surface.
0) is applied circularly by screen printing and then at 80 ℃
It was heated and dried for 30 minutes to form a wall having a height of 8 μm. Further, fixed spacers having a diameter of 9 μm were scattered and attached on the first substrate.

Next, a mixture of polyurethane resin (SP value 8 manufactured by Dainippon Ink and Chemicals, Inc.) and dimethylformamide in a weight ratio of 50:50 was applied to the display portion on the second substrate in a dot shape by screen printing, After drying at 140 ° C. for 1 hour, a columnar structure having a height of 15 μm and a diameter of 50 μm and having a substantially columnar shape was formed in a grid-like arrangement with a pitch of 300 μm.

Further, the epoxy adhesive is applied in a ring shape by screen printing on the second substrate so as to correspond to the sealing material wall pattern on the first substrate, and is heated and dried at 80 ° C. for 30 minutes, A sealing material wall having a thickness of 8 μm was formed.

Then, after applying the liquid crystal composition dl on the second substrate in an amount calculated from the height of the final sealing material and the area inside thereof, the second substrate is pressurized and heated to the second substrate.
It was attached to a substrate and heated at 150 ° C. for 1 hour to prepare a liquid crystal cell (liquid crystal display element) C41.

Next, the same procedure as in the liquid crystal cell C41 was performed except that the fixing spacer had a diameter of 6 μm, the height of the sealing material wall provided on each substrate was 6 μm, and the height of the columnar structure was 12 μm. A liquid crystal cell C42 containing the liquid crystal composition d2 was produced.

The liquid crystal cell C41 is the same as the liquid crystal cell C41 except that the fixing spacer has a diameter of 4 μm, the height of the sealing material wall provided on each substrate is 4 μm, and the height of the columnar structure is 8 μm. Liquid crystal cell C containing composition d3
43 was produced.

These three types of liquid crystal cells C41, C42,
C43 was laminated in this order with a transparent adhesive, and a black light absorbing layer was provided on the back surface of the laminate (the substrate on the side opposite to the side on which light is incident, that is, the outer surface (back surface) of the liquid crystal cell C41).

A predetermined pulse voltage was applied to bring the liquid crystal cell into a colored state and a decolored state. The pulse voltage applied for coloring / decoloring at this time has a pulse width of 5 msec.
Then, the voltage value is cell C41: 40V / 25V, cell C4
It was 2: 29V / 20V and cell C43: 25V / 15V. Further, the Y value during color display was 29.8, the Y value during black display was 3.5, and the contrast was 8.5: 1, indicating good color / black display characteristics.

Such a multi-layer liquid crystal display device was prepared at 80 ° C. for 25 hours.
After heating for a period of time, the display characteristics were measured, and there was no change from that before heating, and it was confirmed that the device had high reliability.

Further, the adhesive strength of the seal portions of the liquid crystal cells C41, C42 and C43 was measured by a 180 ° peel test, and they were 10.1 gf / mm and 10.6 gf / m, respectively.
m was 11.0 gf / mm, and the strength was sufficient to maintain the cell gap.

Example 5 A liquid crystal composition al (SP value of about 9) was prepared in the same manner as in Example 1, and the first and second P
An insulating film and an alignment stabilizing film were formed on the C substrate. And
On the first substrate, the same fixed spacer having a diameter of 6 μm as above was sprayed and attached.

Subsequently, an ultraviolet curable adhesive (Toagosei Co., Ltd., SP value 10) was annularly applied by screen printing on the peripheral portion of the first substrate surface, and dried by heating at 100 ° C. for 1 hour.
A wall with a height of 5 μm was formed.

Next, a mixture of polyurethane resin (SP value 8 manufactured by Dainippon Ink and Chemicals, Inc.) and dimethylformamide in a weight ratio of 50:50 was applied in a dot form by screen printing to the display portion on the second substrate, After drying at 140 ° C. for 1 hour, a columnar structure having a height of 10 μm and a diameter of 50 μm and having a substantially columnar shape was formed in a grid-like arrangement with a pitch of 300 μm.

Further, the ultraviolet curable adhesive was applied in a ring shape by screen printing so as to correspond to the seal material wall pattern on the first substrate, and was dried by heating at 100 ° C. for 1 hour to form a wall having a height of 5 μm. Was formed.

After that, an amount of the liquid crystal composition al calculated on the second substrate was calculated from the height of the final sealing material and the inner area thereof.
After applying, the first substrate is attached to the second substrate while being pressed and heated, and ultraviolet rays are irradiated from a high pressure mercury lamp (300
The sealing material was cured with 0 mJ / cm ² ) to prepare a liquid crystal cell C5. Further, a black light absorption layer was provided on the substrate on the side opposite to the side on which light was incident.

A predetermined pulse voltage was applied to bring the liquid crystal cell C5 into a colored state and a decolored state. The pulse voltage applied for coloring / decoloring at this time has a pulse width of 5 msec.
The voltage value was 33V / 15V. Further, the Y value during color display was 28.8, the Y value during black display was 1.6, and the contrast was 18: 1, and the device was a device having a high contrast with good color / black display characteristics.

After the liquid crystal cell C5 was heated at 80 ° C. for 25 hours and the display characteristics were measured, there was no change from that before heating.
It was confirmed to be a highly reliable element. Further, the adhesive strength of the sealing material portion of the liquid crystal cell C5 was measured by a 180 ° peeling test, and was 5 gf / mm, which was a sufficient strength to hold the cell gap.

Example 6 Next, a production example of a polymer dispersion type liquid crystal display device will be described. First, as in the first embodiment, the first,
An insulating film and an alignment stabilizing film were formed on a second polycarbonate (PC) substrate. A rubbing treatment was applied to the alignment stabilizing film.

Subsequently, the same epoxy adhesive as in Example 3 (manufactured by Mitsui Chemicals, SP value 1) was applied to the peripheral portion of the first substrate surface.
0) is circularly applied by screen printing, and is applied at 80 ° C for 3
It was dried by heating for 0 minutes to form a wall having a height of 10 μm. In addition, fixed spacers having a diameter of 10 μm were scattered and attached on the first substrate.

Further, the epoxy-based adhesive is annularly applied by screen printing on the second substrate so as to correspond to the seal material wall pattern on the first substrate, and the epoxy adhesive is applied at 80 ° C. for 3 hours.
It was dried by heating for 0 minutes to form a wall having a height of 10 μm.

Refractive index anisotropy Δn: 0.254, different dielectric constant
Isotropic Δε: 20, isotropic phase transition temperature T _NI: 70 ℃, SP
Value: 9 nematic liquid crystal C (SP value: 9) and acrylic
Monomer (R684, manufactured by Merck) and photopolymerization initiator (a)
(Lugacure 184, manufactured by Nagasetiva Co., Ltd.) in a weight ratio of 80:
Mix at 17: 3 to prepare the liquid crystal / polymer precursor mixture fl.
Made

After that, after applying the liquid crystal / polymer precursor mixture fl on the second substrate in an amount calculated from the height of the final sealing material and the inner area thereof, the first substrate is pressurized and heated while Two substrates were stuck together. Next, ultraviolet rays were irradiated at 6000 mJ / cm ² with a high pressure mercury lamp to polymerize the acrylic monomer to prepare a polymer dispersion type liquid crystal cell (liquid crystal display element) C6. Further, polarizing plates were provided on both sides of the liquid crystal cell C6 so as to be orthogonal to each other.

The liquid crystal cell C6 was in an opaque state when no voltage was applied, and became transparent by applying a voltage of 9V. The transmitted light intensity contrast ratio was 15: 1, and the device was a good device with high contrast.

When the liquid crystal cell C6 was heated at 80 ° C. for 25 hours and then the display characteristics were measured, there was no change from that before heating, and it was confirmed that the device had high reliability. Also,
When the adhesive strength of the sealing material portion of the liquid crystal cell C6 was measured by the 180 ° peeling test, it was 10.3 gf / mm, which was a sufficient strength to hold the cell gap.

Example 7 Next, a production example of a polymer dispersion type ferroelectric liquid crystal display device will be shown. Similar to the first embodiment,
An insulating film and an alignment stabilizing film were formed on the first and second polycarbonate (PC) substrates. A rubbing treatment was applied to the alignment stabilizing film.

Subsequently, the same epoxy adhesive as in Example 3 (manufactured by Mitsui Chemicals, SP value 1) was applied to the peripheral portion of the first substrate surface.
0) is circularly applied by screen printing, and is applied at 80 ° C for 3
It was dried by heating for 0 minutes to form a wall having a height of 6 μm. Also,
On the first substrate, fixed spacers having a diameter of 7 μm were scattered and attached.

Further, the epoxy-based adhesive is annularly applied by screen printing on the second substrate so as to correspond to the seal material wall pattern on the first substrate, and the epoxy adhesive is applied at 80 ° C. for 3 hours.
It was dried by heating for 0 minutes to form a wall having a height of 6 μm.

A ferroelectric liquid crystal having an SP value of 9, an acrylic monomer (R684, manufactured by Merck), and a photopolymerization initiator (Irgacure 184, manufactured by Nagasetiva) were mixed at 80: 17: 3 to prepare a liquid crystal / polymer. A precursor mixture gl was prepared.

Then, after applying the liquid crystal / polymer precursor mixture gl on the second substrate in an amount calculated from the height of the final sealing material and the inner area thereof, the first substrate is pressed and heated. It was bonded to the second substrate. Next, ultraviolet rays were irradiated at 6000 mJ / cm ² with a high pressure mercury lamp to polymerize the acrylic monomer to prepare a polymer dispersion type liquid crystal cell (liquid crystal display element) C7. Further, polarizing plates were provided on both sides of the liquid crystal cell C7 so as to be orthogonal to each other.

The liquid crystal cell C7 was changed from an opaque state to a transparent state by applying a pulse voltage of 10 V, and -1
It became opaque again by applying a pulse voltage of 0V. At this time, the contrast ratio of the transmitted light intensity was 14: 1, and the device was a good device with high contrast.

The liquid crystal cell C7 was heated at 80 ° C. for 25 hours and then the display characteristics were measured.
It was confirmed to be a highly reliable element. Further, the adhesive strength of the sealing material portion of the liquid crystal cell C7 was measured by a 180 ° peeling test, and it was 10.5 gf / mm, which was a sufficient strength to hold the cell gap.

Comparative Example 1 In the above Example 2,
In forming the board-to-board sealant, a silicone adhesive (Toray Dow Corning Silicone, SP value 7.5) was screen printed only on the first board.
A liquid crystal cell Cll was prepared in the same manner as in Example 2. The display characteristics of the liquid crystal cell C1 and the display characteristics after heating at 70 ° C. for 25 hours were the same as those of Example 2, but the adhesive strength of the sealing material portion was measured by the 180 ° peel test to be 1 gf / mm or less. However, the strength capable of maintaining the cell gap was not obtained. This is because the liquid crystal material was narrowed between the sealing material and the second substrate, and the adhesive area was significantly reduced.

Comparative Example 2 A liquid crystal cell was prepared in the same manner as in Example 1 except that the resin material used as the sealing material in Example 1 was changed to a polyurethane resin having an SP value of 9 (manufactured by Dainippon Ink and Chemicals, Inc.). C12 was produced. Liquid crystal cell C
The voltage for changing the colored state of 12 to the decolored state is 32 V /
It was 16 V and the driving voltage was high. The Y value during color display was 29.0, the Y value during black display was 1.9, and the contrast was 15.3: 1. Liquid crystal cell C12 at 80 ° C
When the display characteristics were measured after heating at 25 ° C. for 25 hours, the Y value at the time of coloring was reduced by 10%. When the SP values of the sealing material and the liquid crystal composition are close to each other, the liquid crystal composition melts the sealing material, so that the characteristics of the liquid crystal display element deteriorate.
The adhesive strength of the sealing material portion of the liquid crystal cell C12 was equivalent to that in Example 1.

In each of Examples 1 to 3 and Example 5, an example was shown in which a liquid crystal display device was produced using a liquid crystal composition capable of displaying a visible light color near a specific wavelength. A liquid crystal display element for use in the same manner can be manufactured in the same manner, and a liquid crystal display element for at least red, green, and blue is manufactured, and by stacking these, a multilayer liquid crystal display element capable of full-color display can be manufactured. You can also

Next, some examples (Examples 8 to 10) of a method for manufacturing a liquid crystal display device by adhering a substrate connection support material to each of a pair of substrates will be described, and a comparative example (Comparative Example 3). ) Is also described, and the evaluation results are also described. In each of the liquid crystal display elements of Examples and Comparative Examples described below, a light absorbing layer was finally formed on the outer surface of the second substrate opposite to the image observation side. The invention is not limited to these examples.

Each of the liquid crystal display elements described below was basically prepared by adopting the method shown in FIG. 10 in which the liquid crystal composition is placed between the substrates and the two substrates are bonded together.
As the liquid crystal composition, as in Example 1, 31.5 parts by weight of a chiral material (S-811 manufactured by Merck & Co., Inc.) was added to 68.5 parts by weight of the nematic liquid crystal mixture A, and 560
A chiral nematic liquid crystal composition al that selectively reflects light having a wavelength near nm was prepared.

(Embodiment 8) Similar to Embodiment 1, the insulating film and the alignment stabilizing film were formed on the first and second PC substrates provided with the ITO transparent electrodes in advance. Before the insulating film was formed, the surface of the substrate having the electrodes was washed.

Organic solvents (dimethyl adipate and DMF)
A columnar structure material (substrate connecting support material) made of a polyurethane resin (STAYSTIK371G manufactured by Alpha Metals Co., Ltd.) whose viscosity is adjusted in step 1 is provided under the following conditions on the alignment stabilizing film of each of the first and second substrates. did. Arrangement method: Screen printing used Printing plate: 20 μm diameter holes pitch pt ′ = 450 μ
Stainless plates arranged in a grid array with m (see FIG. 4) Resin viscosity: 80 Pa · s (cone plate type rotational viscometer, measured at a shear rate of 50 [1 / s]) Drying condition: 140 ° C. for 1 hour

The shape of the columnar structure material after drying on each substrate was measured by three-dimensional non-contact surface shape measurement using a Michelson interferometer (Micromap manufactured by Ryoka System), and the diameter D _{1 of} the bottom surface was measured. = 27 μm, maximum height H ₁ =
It had a mountain shape of 3.7 μm (see FIG. 5).

After that, a silica spacer having a particle size of 5 μm coated with a thermoplastic resin is sprinkled on the first substrate, and the temperature is set to 140 ° C.
Then, the spacer was fixed to the first substrate by heating in the oven for 30 minutes. The second substrate is screen-printed with a thermosetting sealing material in an annular shape and heated in an oven at 130 ° C. to a height of 10
Temporarily cured to a μm wall.

After the sealing material is temporarily cured, the liquid crystal composition is supplied to the first substrate, and the first and second substrates are stored at room temperature as shown in FIG.
In the same manner as above, the substrates were sequentially superposed from the ends. In this state, the columnar structure materials on both substrates are butted against each other. Since the bottom diameter of each columnar structure material is 27 μm,
If the positional accuracy at the time of superposition is within ± 13 μm, the columnar structure materials can be sufficiently abutted with each other.
If they are butted with each other without deviation, the state shown in FIG.

Then, the substrate pair superposed on the flat table surface heated to 130 ° C. was fixed, and a roller heated to 60 ° C. was passed therethrough while being pressurized at 0.25 Pa. Through this step, the columnar structures facing each other were fused together, and at the same time, the height of the sealing material and the columnar structures was set to the value of the gap between both substrates determined by the spacer diameter.

Both substrates thus bonded are further
Bake in an oven at 0 ° C for 3 hours to cure the sealing material,
A liquid crystal display device was obtained. Observing the columnar structure after element formation with an optical microscope, the contact surface (bonding surface) with the substrate has a diameter D.
₂ = 30 μm, misalignment of upper and lower columnar structure materials dx = 1
It was 0 μm, which was small as about 900 μm ² as a non-display area by one columnar structure (see FIG. 6B).

Further, in order to measure the strength of the element against the bulging pressure, a tensile compression tester (SV-3 manufactured by IMADA) was used.
01 type) was used for tensile test, the device was 1 cm
^{2 It} showed a tensile strength of 300 gf. Further, when the substrate after peeling was observed, it was found that the residual ratio of the columnar structure portion was substantially equal in both substrates, and not only peeling at the bonding surface with the substrate but also cohesive failure in the columnar structure itself occurred. It was This shows that the columnar structure (substrate connecting support) has a large bonding force between both substrates.

(Embodiment 9) Similar to Embodiment 8, the insulating film and the alignment stabilizing film are formed on the first and second PC substrates provided with the ITO transparent electrodes in advance, and the alignment stabilizing film is formed on the alignment stabilizing film. The columnar structure material was provided on the first substrate, the spacer was fixed to the first substrate, the sealing material was provided on the second substrate, and the second substrate was provisionally cured.

After the sealant was temporarily cured, the liquid crystal composition was supplied to the first substrate, and the first and second substrates were laminated in the thermostatic chamber at 60 ° C. as in Example 8. At this time, the columnar structure materials on both substrates were butted against each other. Since both substrates were superposed in the constant temperature layer at 60 ° C. in this way, both substrates thermally expanded to the same extent, and the positional displacement due to the strain of the substrates during superposition was small.

Then, the inside of the temperature-controlled room was set to a temperature equal to or higher than the softening temperature of the columnar structure material, and both substrates were bonded with a roller under a pressure of 0.25 Pa as in the case of Example 8. As a result, the heights of the sealing material and the columnar structure were set to the value of the gap between the two substrates, which was determined by the spacer diameter, at the same time when the columnar structure materials on both the substrates were fused.

The both substrates thus bonded were further baked in an oven at 80 ° C. for 3 hours to cure the sealing material to obtain a liquid crystal display element. When observing the columnar structure after element formation with an optical microscope, the contact surface (bonding surface) with the substrate has a diameter D ₂ = 30 μm.
m, the positional deviation of the upper and lower columnar structures dx = 2 μm, and the non-display area by one columnar structure is about 800.
It was as small as μm ² (see FIG. 6B).

Further, in order to measure the strength of the element against the bulging pressure, a tensile compression tester (SV-3 manufactured by IMADA) was used.
01 type) was used for tensile test, the device was 1 cm
A tensile strength of 320 gf per ² was shown. Further, when the substrate after peeling was observed, it was found that the residual ratio of the columnar structure portion was almost equal in both substrates, and not only peeling at the bonding surface with the substrate but also cohesive failure in the columnar structure itself occurred. It was This shows that the columnar structure (substrate connecting support) has a large bonding force between both substrates.

(Example 10) In this example, a columnar structure was formed of a thermosetting resin as a substrate connecting support disposed in the display area, and the same material was used as a sealing material for enclosing a liquid crystal composition. This is an example.

First, similarly to the first embodiment, ITO was previously prepared.
An insulating film and an alignment stabilizing film were formed on the first and second PC substrates provided with transparent electrodes. Before the insulating film was formed, the surface of the substrate having the electrodes was washed.

Next, a silica spacer having a particle size of 5 μm and coated with a thermoplastic resin is sprinkled on the alignment stabilizing film of the first substrate and heated in an oven at 140 ° C. for 30 minutes to fix the spacer to the first substrate. Let

Next, using an epoxy resin (Structbond XLC260 manufactured by Mitsui Chemicals, Inc.) having methyl carbitol as a solvent as the columnar structure material and the sealing material, the alignment stabilizing films of the first and second substrates were used. The columnar structure material and the sealing material were formed on the above under the following conditions. Arrangement method: Screen printing printing plate: 20 μm diameter holes pitch pt ″ = 450 μ
A stainless steel plate having a mesh portion which is arranged in a grid array at m intervals and annularly surrounds the region having the holes with a width of 40 μm (see FIG. 7) Resin viscosity: 70 Pa · s (cone plate type rotational viscometer, shear rate 50 [Measurement at [1 / s]) Temporary curing condition: After drying at 80 ° C. for 20 minutes, temporary curing at 130 ° C. for 8 minutes

The shape of the temporarily cured columnar structure material was measured by three-dimensional non-contact surface shape measurement using a Michelson interferometer (Micromap manufactured by Ryoka Systems Co., Ltd.), and the diameter D _{1 of} the bottom surface was D ₁ = 35 μm. Maximum height H ₁ = 3.2
It had a mountain shape of μm (see FIG. 5).

After the sealant was temporarily cured, the liquid crystal composition was supplied to the first substrate, and the first and second substrates were laminated at room temperature in the same manner as in Example 8. In this state, the columnar structure materials on both substrates are butted against each other. Since the bottom diameter of each columnar structure material is 35 μm, the columnar structure materials can be sufficiently abutted with each other if the positional accuracy at the time of superposition is within ± 17 μm.

Next, at room temperature, the pair of substrates superposed on the flat base surface was fixed, and a roller was placed thereon for 0.25 Pa.
It was passed under pressure. Through this step, the columnar structures facing each other were bonded together, and at the same time, the height of the sealing material and the columnar structures was set to the value of the gap between the two substrates determined by the spacer diameter.

The both substrates which were bonded together were further baked in an oven at 80 ° C. for 3 hours to cure the sealing material to obtain a liquid crystal display element. Observing the columnar structure after element formation with an optical microscope, the contact surface (bonding surface) with the substrate has a diameter D ₂ = 35 μm.
m, the positional deviation of the upper and lower columnar structure materials was dx = 10 μm, and the non-display area by one columnar structure was as small as about 1000 μm ² (see FIG. 6B).

Further, in order to measure the strength of the element against the bulging pressure, a tensile compression tester (SV-3 manufactured by IMADA) was used.
01 type) was used for tensile test, the device was 1 cm
The tensile strength of 450 gf per ² was shown. Further, when the substrate after peeling was observed, it was found that the residual ratio of the columnar structure portion was substantially equal in both substrates, and not only peeling at the bonding surface with the substrate but also cohesive failure in the columnar structure itself occurred. It was This shows that the columnar structure (substrate connecting support) has a large bonding force between both substrates.

COMPARATIVE EXAMPLE 3 This comparative example is an example in which a columnar structure is formed of a thermoplastic resin as a substrate connecting support disposed in the display area.

First, in the same manner as in Example 8, ITO was previously prepared.
An insulating film and an alignment stabilizing film were formed on the first and second PC substrates provided with transparent electrodes. Before the insulating film was formed, the surface of the substrate having the electrodes was washed.

Next, an organic solvent (dimethyl adipate and D
A columnar structure material (substrate connection support material) made of a polyurethane resin (STAYSTIK371G manufactured by Alpha Metals Co., Ltd.) whose viscosity was adjusted by MF) was arranged under the following conditions only on the alignment stabilizing film of the second substrate. Arrangement method: Screen printing printing plate: Stainless plate resin in which holes of 100 μm diameter are arranged in a lattice pattern at 450 μm intervals Viscosity: 80 Pa · s (cone plate type rotational viscometer, measured at a shear rate of 50 [1 / s]) ) Drying conditions: 140 ° C for 1 hour

The shape of the columnar structure after drying was measured by a three-dimensional non-contact surface shape measuring system (Micromap Ryoka System) using a Michelson interferometer, and it was found that the diameter D ₁ ′ of the bottom surface was 115 μm. Maximum height H ₁ '=
It had a peak shape of 6.2 μm (see FIG. 8).

On the other hand, a silica spacer having a particle diameter of 5 μm coated with a thermoplastic resin was scattered on the first substrate and heated in an oven at 140 ° C. for 30 minutes to fix the spacer to the substrate. After that, a thermosetting sealing material is screen-printed on the first substrate in an annular shape and heated in an oven at 130 ° C. to a height of 1
It was temporarily cured on a 0 μm wall.

After the sealing material was temporarily cured, the liquid crystal composition was supplied onto the first substrate, and the first and second substrates were superposed at room temperature. Next, the pair of substrates superposed on the flat base surface heated to 130 ° C. is fixed, and a roller is placed on the substrate.
The two substrates were bonded to each other while being passed under pressure at 25 Pa. Through this step, the heights of the sealing material and the columnar structure were set to the value of the gap between the two substrates determined by the spacer diameter.

The both substrates thus bonded were further baked in an oven at 80 ° C. for 3 hours to cure the sealing material to obtain a liquid crystal display element. When the columnar structure after element formation is observed with an optical microscope, the contact surface (bonding surface) with the substrate is the diameter D on the second substrate.
₂ ′ = 115 μm, the diameter D ₂ ″ = 90 μm on the first substrate, and the non-display area by one columnar structure was as large as about 10,400 μm ² (see FIG. 9).

Further, in order to measure the strength of the element against the bulging pressure, a tensile compression tester (SV-3 manufactured by IMADA) was used.
01 type) was used for tensile test, the device was 1 cm
A tensile strength of 80 gf per ² was shown. Further, when the substrate after peeling is observed, it can be seen that most of the columnar structure remains on the second substrate, and the columnar structure is peeled at the contact surface with the second substrate. This gives a columnar structure (substrate connection support)
It can be seen that the binding force of both substrates due to is weak.

In each of Examples 8 to 10, an example of producing a liquid crystal display element using a liquid crystal composition capable of displaying a visible light color near a specific wavelength was shown, but a liquid crystal display for display of other colors is shown. A device can be manufactured in the same manner, and a liquid crystal display device for at least red, green, and blue is manufactured, and by stacking these, a laminated liquid crystal display device capable of full-color display can be manufactured.

[0207]

As described above, according to the present invention, there is provided a method of manufacturing a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates. A method capable of obtaining a high liquid crystal display device can be provided. More specifically, it is as follows.

(1) According to the present invention, there is provided a method of manufacturing a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates and the pair of substrates are bonded together by a sealing material surrounding the liquid crystal composition. As a result, it is possible to provide a method in which the bonding strength of both substrates by the sealing material is high and a liquid crystal display element having high reliability can be obtained.

(2) Further, according to the present invention, the liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are connected to each other by a substrate connection support disposed between the pair of substrates. It is possible to provide a method for manufacturing a liquid crystal display element, wherein the substrate connection support has a high adhesive strength with any substrate, and a liquid crystal display element having high reliability can be obtained.

According to the present invention, there is further provided a method for producing a liquid crystal display device, in which a liquid crystal composition is sandwiched between a pair of substrates and the pair of substrates are bonded by a sealing material surrounding the liquid crystal composition, It is also possible to provide a method capable of producing a liquid crystal display device by suppressing the elution of the sealing material component into the liquid crystal composition, and thereby obtaining a liquid crystal display device capable of displaying a high quality image.

According to the present invention, further, a liquid crystal display device in which a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are mutually connected by a substrate connecting support disposed between the pair of substrates. It is also possible to provide a method for producing a liquid crystal display element, which is capable of obtaining a liquid crystal display element without fear that the aperture ratio is significantly lowered due to the presence of the substrate connection support.

Further, according to the present invention, it is possible to provide a highly reliable multilayer liquid crystal display element in which each liquid crystal display element is formed by adopting at least one of the above methods.

[Brief description of drawings]

1A and 1B are schematic cross-sectional views of an example of a multi-layer liquid crystal display device, FIG. 1A showing a planar state, and FIG. 1B showing a focal conic state.

FIG. 2 is a diagram showing an example in which a sealing material is attached in a ring shape on a substrate.

FIG. 3 is a diagram showing an example in which a substrate connection support material is attached in a dot shape on a substrate.

FIG. 4 is a plan view showing an example of a printing plate for screen printing of a substrate connection support material.

FIG. 5 is a diagram showing a bottom diameter and a maximum height of a substrate connection support material on one side substrate when the substrate connection support material is attached to each of the pair of substrates.

FIG. 6 is a diagram showing an example of a columnar structure formed by adhering substrate connection support materials on a pair of substrates, and FIG.
Shows the case where there is no deviation between the materials, and FIG. 9B shows the case where there is a deviation between the materials.

FIG. 7 is a plan view showing another example of the printing plate for screen printing of the substrate connection support material.

FIG. 8 is a diagram showing a bottom surface diameter and a maximum height of a substrate connection support material when the substrate connection support material is attached only on one of the substrates.

9 is a diagram showing an example of a columnar structure formed by bonding one substrate shown in FIG. 9 to the other substrate.

FIG. 10 is a diagram illustrating an example in which a liquid crystal composition is placed between a pair of substrates and the two substrates are bonded together.

FIG. 11 is a diagram showing a state in which the substrate connection support material arranged on the substrate has a mountain shape.

[Explanation of symbols]

R Red liquid crystal display element G Green liquid crystal display element B Blue liquid crystal display element N adhesive layer 11, 12 substrate 18 Spacer 20 Substrate connection support (columnar structure) 24 Seal material 21r Liquid crystal composition for red display 21 g Liquid crystal composition for green display 21b Liquid crystal composition for blue display 13, 14 electrodes 15 Insulating thin film 16a, 16b Alignment stabilizing film 17 Visible light absorption layer 25 pulse application device

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Makiko Tango             2-3-3 Azuchi-cho, Chuo-ku, Osaka-shi, Osaka Prefecture               Osaka International Building Minolta Co., Ltd. (72) Inventor Keiichi Furukawa             2-3-3 Azuchi-cho, Chuo-ku, Osaka-shi, Osaka Prefecture               Osaka International Building Minolta Co., Ltd. F-term (reference) 2H089 HA04 HA23 HA32 LA07 LA09                       LA12 LA41 NA08 NA24 NA32                       NA41 NA44 PA01 PA16 QA02                       RA06 TA06

Claims (5)

[Claims] 1. A method of manufacturing a liquid crystal display device, wherein a liquid crystal composition is sandwiched between a pair of substrates, and the pair of substrates are bonded together by a sealing material surrounding the liquid crystal composition. A seal material attaching step of attaching an uncured seal material to the first substrate and attaching an uncured seal material made of the same material as the second substrate among the pair of substrates to the second substrate; A substrate bonding step of bonding and bonding the pair of substrates to each other by bonding and bonding the sealing material, and a liquid crystal composition can be placed between the substrates while spreading the liquid crystal composition between the pair of substrates in the bonding step. Or before supplying the substrate, the liquid crystal composition is supplied to at least one of the surfaces of the pair of substrates which should face each other,
Or a liquid crystal supply step of supplying a liquid crystal composition between the pair of substrates after the substrate bonding step, wherein the adhesion of the seal material to the first and second substrates in the seal material adhesion step is performed by the first step. A method for manufacturing a liquid crystal display device, wherein the sealing material adhered to the substrate and the sealing material adhered to the second substrate are overlapped with each other in the substrate adhering step as a whole or substantially as a whole. 2. The liquid crystal composition and the sealing material, wherein the solubility parameter δ _LC of the liquid crystal composition and the solubility parameter δ _R of the sealing material are δ _R ≦ δ _LC −1 or δ _R ≧ δ _LC +
1. A method of manufacturing a liquid crystal display device, which comprises using a liquid crystal composition and a sealant satisfying the relationship of 1. 3. A substrate connecting support, wherein a liquid crystal composition and a sealing material surrounding the liquid crystal composition are sandwiched between a pair of substrates, and the substrate connecting support is arranged between the pair of substrates and in a region surrounded by the seal. A method of manufacturing a liquid crystal display element in which the pair of substrates are connected to each other in a body, a step of disposing a sealing material on at least one of the pair of substrates, and a first substrate of the pair of substrates. A polymer material attaching step of attaching an uncured polymer material as the connection support material, while attaching an uncured polymer material as the connection support material to a second substrate of the pair of substrates; A substrate bonding step in which the substrates are adhered to each other and the polymer materials are bonded and bonded to each other; and in the substrate bonding step, the liquid crystal composition is spread between the pair of substrates and arranged between the substrates. So that the liquid crystal composition is supplied to at least one of the surfaces of the pair of substrates that should face each other before the substrate bonding step, or the liquid crystal composition is provided between the pair of substrates after the substrate bonding step. A liquid crystal supplying step of supplying a substance, wherein the adhesion of the polymer material to the first and second substrates in the polymer material attaching step includes the step of attaching the polymer material to the first substrate and the second material. A method of manufacturing a liquid crystal display device, wherein the polymer material attached to the substrate is overlapped in the attaching step. 4. The method of manufacturing a liquid crystal display device according to claim 3, wherein the polymer material is a thermoplastic polymer material. 5. A multi-layer liquid crystal display device, characterized in that a multi-layer liquid crystal display device is obtained by laminating a plurality of liquid crystal display devices manufactured by the method for manufacturing a liquid crystal display device according to any one of claims 1 to 4. Device manufacturing method.