JPH10293328A - Method for manufacturing reflective guest-host liquid crystal display device - Google Patents

Abstract

(57) Abstract: In a method of manufacturing a reflection type guest-host liquid crystal display device, an alignment layer of liquid crystal is formed thereon without damaging a quarter-wave plate layer. A light reflection layer is formed on a substrate.
A quarter-wave plate layer 9 made of a uniaxially oriented polymer liquid crystal is formed on the light reflection layer 8. The pixel electrode 11 is formed on the quarter-wave plate layer 9. Further, the pixel electrode 11
A vertical alignment agent using triethylene glycol dimethyl ether as a solvent is applied on the quarter-wave plate layer 9 exposed between the pixel electrodes 11 to form an alignment layer 12.
Thereafter, the substrate 1 on which the counter electrode 6 is formed in advance is bonded to the substrate 2 via a predetermined gap. Finally, a guest-host liquid crystal 3 containing a dichroic dye is injected into the gap between the substrates 1 and 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a reflection type guest-host liquid crystal display device. More specifically, the present invention relates to a technology for improving the utilization efficiency of incident light by forming a quarter-wave plate layer as a polarization conversion element in a panel. More specifically, the present invention relates to a technique for stably forming an alignment layer on a quarter-wave plate layer having poor solvent resistance.

[0002]

2. Description of the Related Art A reflection type guest-host liquid crystal display device having a quarter-wave plate layer built in a panel as a polarization conversion element is known, and is disclosed, for example, in Japanese Patent Application Laid-Open No. 6-222351. As shown in FIG. 7, the guest-host liquid crystal display device 101 is assembled using a pair of upper and lower substrates 102 and 103. A pair of substrates 102 and 10
Numeral 3 is made of an insulating material such as glass, quartz, plastic, or the like, and at least the upper substrate 102 has transparency. A guest-host liquid crystal 104 including a nematic liquid crystal molecule 104a and a dichroic dye 105 is interposed between the substrates 102 and 103. The dichroic dye 105 is a p-type dye having a transition dipole moment substantially parallel to the long axis of the molecule. Inner surface 102a of upper substrate 102
Although not shown, a switching element including a two-terminal element such as an MIM or a three-terminal element such as a TFT and the pixel electrode 106 are formed. Inner surface 10 of upper substrate 102 on which switching elements and pixel electrodes 106 are formed
2a, an alignment layer 10 made of a polyimide resin or the like is further provided.
7 is formed. The surface of the alignment layer 107 has been subjected to a rubbing process in order to horizontally align the nematic liquid crystal molecules 104a. On the other hand, the inner surface 10 of the lower substrate 103
3a, a light reflection layer 108 and a quarter-wave plate layer 109 are formed in this order. The quarter-wave plate layer 109 is made of a uniaxially oriented polymer liquid crystal. This is formed by heating a polymer liquid crystal and attaching it to a separately heated or cooled substrate 103. On the surface of the quarter-wave plate layer 109, a counter electrode 110 and an alignment layer 111 are formed in this order. The alignment layer 111 is made of a polyimide resin or the like similarly to the upper alignment layer 107, and its surface is subjected to a rubbing treatment.

[0005] Next, the operation of the reflective guest-host liquid crystal display device 101 for monochrome display will be briefly described. When no voltage is applied, the liquid crystal molecules 104a are horizontally aligned along the rubbing direction of the upper and lower alignment layers 107 and 111, and the dichroic dye 105 is similarly aligned. When light incident from the upper substrate 102 side passes through the guest-host liquid crystal 104, a component of the incident light having a vibration plane parallel to the major axis direction of the molecules of the dichroic dye 105 becomes a dichroic dye 1
05 is absorbed. Other components having a vibration plane perpendicular to the major axis direction of the molecules of the dichroic dye 105 pass through the guest-host liquid crystal 104 and form a quarter formed on the inner surface 103a of the lower substrate 103. The light is circularly polarized by the one-wavelength plate layer 109 and is reflected by the light reflecting layer 108. At this time, the polarization of the reflected light is reversed, and again the quarter-wave plate layer 109
And is converted into light having a vibration plane parallel to the major axis direction of the molecules of the dichroic dye 105. Since this light is absorbed by the dichroic dye 105, almost complete black display is obtained. On the other hand, when a voltage is applied, the nematic liquid crystal molecules 10
4a are oriented vertically along the direction of the electric field, and the dichroic dye 10
5 is similarly oriented. Light incident from the upper substrate 102 side passes through the guest-host liquid crystal 104 without being absorbed by the dichroic dye 105, and passes through the light reflection layer 108 without being substantially affected by the quarter-wave plate layer 109. reflect.
The reflected light passes through the quarter-wave plate layer 109 again and exits without being absorbed by the guest-host liquid crystal 104. Therefore, white display is obtained.

[0004]

In the conventional structure shown in FIG. 7, a uniaxially oriented polymer liquid crystal is used as a quarter-wave plate layer. This polymer liquid crystal has relatively poor solvent resistance,
It easily dissolves or swells in a polar solvent or the like and loses uniaxial orientation. Generally, an orientation layer 111 for the guest host 104 is formed on the quarter-wave plate layer 109. For example, an alignment agent in which a polyimide resin is dissolved in a solvent such as n-methyl-2-pyrrolidone (NMP) or γ-butyrolactone is applied, and the solvent is evaporated to form an alignment layer 111 made of the polyimide resin. In this case, the polymer liquid crystal constituting the quarter-wave plate layer 109 may be dissolved in the solvent contained in the alignment agent, and the uniaxial anisotropy may be lost. Therefore, in the conventional structure, there was no alternative but to use a water-soluble alignment agent using polyvinyl alcohol (PVA) as a practical means. However, as shown in FIG. 7, the alignment layer made of PVA can horizontally align the liquid crystal molecules 104a, but cannot vertically align the liquid crystal molecules 104a. From the viewpoint of display quality, the vertical alignment type guest-host liquid crystal display device was not able to be realized in spite of being superior in contrast and the like as compared with the horizontal alignment type guest-host liquid crystal display device. That is, since the choice of the alignment agent is limited due to the solvent resistance of the quarter-wave plate layer, it has been difficult to produce a vertical alignment type guest-host liquid crystal display device by a practical process. .

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems of the prior art, the following measures have been taken. That is, the reflection type guest-host liquid crystal display device is manufactured by the following steps according to the present invention. First, in a first step, a light reflection layer is formed on a first substrate. In the second step, a quarter-wave plate layer made of a uniaxially oriented polymer liquid crystal is formed on the light reflecting layer.
In a third step, an electrode is formed on the quarter-wave plate layer. In a fourth step, an alignment layer is formed by applying a vertical alignment agent using triethylene glycol dimethyl ether as a solvent on the electrodes and on the quarter wave plate layer exposed between the electrodes. In a fifth step, a second substrate on which electrodes are formed in advance is joined to the first substrate via a predetermined gap. In a sixth step, a guest-host liquid crystal containing a dichroic dye is injected into the gap.

Preferably, in the fourth step, a vertical alignment agent obtained by dissolving polyamic acid or polyimide in triethylene glycol dimethyl ether is applied. Preferably, in the fourth step, the vertical alignment agent is applied in a state diluted with diethylene glycol diethyl ether. More preferably, the fourth step is performed at 35 ° C. after applying a vertical alignment agent.
Vacuum drying is performed in a temperature range of from about 55 ° C. to about 55 ° C. to form an alignment layer. In the second step, for example, a polymer liquid crystal in which biphenylbenzoate is introduced into a side chain separated from an alkyl main chain is formed to form a quarter-wave plate layer.

In a reflection type guest-host liquid crystal display device having a quarter-wave plate layer incorporated therein, an alignment layer made of polyimide, polyamic acid, or the like is used to regulate the alignment of the guest-host liquid crystal. However, the liquid crystal polymer (liquid crystal polymer) constituting the quarter-wave plate layer has a low solvent resistance in many cases, and is dissolved in the conventionally used solvents of polyimide and polyamic acid such as NMP and γ-butyrolactone. Resulting in. Therefore, in the present invention, triethylene glycol dimethyl ether is used instead of the conventional solvent. This has excellent compatibility with polyimide and polyamic acid, and has lower solubility in the polymer liquid crystal constituting the quarter-wave plate layer than conventional NMP or γ-butyrolactone. . Therefore, by using a vertical alignment agent containing triethylene glycol dimethyl ether as a solvent, a vertical alignment layer can be stably formed thereon without adversely affecting the quarter-wave plate layer.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for manufacturing a reflection type guest-host liquid crystal display device according to the present invention will be described below in detail with reference to the drawings. FIG. 1 is a partial cross-sectional view showing a basic configuration of a reflective guest-host liquid crystal display device. As shown, the reflection type guest-host liquid crystal display device manufactured according to the present invention includes a pair of upper and lower substrates 1 and 2 joined to each other via a predetermined gap and a guest-host liquid crystal 3 held in the gap. I have. The guest-host liquid crystal 3 is mainly composed of nematic liquid crystal molecules 4 and contains a dichroic dye 5. At least the counter electrode 6 is provided on the upper substrate 1 on the incident side.
And the orientation layer 7 are formed in this order.

On the lower substrate 2 on the reflection side, at least a light reflection layer 8, a quarter-wave plate layer 9, a pixel electrode 1
1 and an orientation layer 12 are stacked. The quarter wave plate layer 9 is made of a uniaxially oriented liquid crystal polymer having relatively poor solvent resistance. The alignment layer 12 is formed of an organic coating film coated with an alignment agent and rubbed. The alignment layers 7 and 12 sandwiching the guest host liquid crystal 3 from above and below vertically align the nematic liquid crystal molecules 4, and accordingly, the dichroic dye 5 is vertically aligned. As a characteristic matter, a vertical alignment agent using triethylene glycol dimethyl ether (DMTG) as a solvent is coated on the pixel electrodes 11 and the quarter-wave plate layer 9 exposed between the pixel electrodes 11 to form an alignment layer. 12 is formed. In particular,
A vertical alignment agent obtained by dissolving polyamic acid or polyimide in DMTG is applied to form an alignment layer 12. in this case,
The vertical alignment agent is further diluted by diethylene glycol diethyl ether (DEDG) and applied by spin coating. In some cases, butyl cellosolve (BC) can be used instead of DEDG. After applying the vertical alignment agent having such a composition, preferably 35 ° C. to 55 ° C.
The alignment layer 12 is formed by performing vacuum drying in a temperature range of ° C. In the present embodiment, a quarter-wave plate layer 9 is formed by forming a polymer liquid crystal in which biphenylbenzoate is introduced into a side chain separated from an alkyl main chain.

The reflection type guest-host liquid crystal display device according to the present embodiment is of a so-called active matrix type, and a thin film transistor 13 is formed on the lower substrate 2 as a switching element for driving each pixel electrode 11, for example. . The thin film transistor 13 has a bottom gate structure, and a gate electrode 14, a gate insulating film 15,
The semiconductor thin film 16 and the stopper 17 are stacked.
The interlayer insulating film 1 is formed so as to cover the thin film transistor 13.
8 are formed. A source electrode 19 and a drain electrode 20 are formed thereon by patterning, and are electrically connected to the thin film transistor 13 through a contact hole opened in the interlayer insulating film 18. The light reflection layer 8 is formed on the interlayer insulating film 18. The light reflection layer 8 is subdivided for each pixel corresponding to the pixel electrode 11 and has the same potential as the drain electrode 20. The reflection layer 8 has an uneven light scattering surface, and realizes a display screen called a so-called white paper. A flattening layer 21 is formed so as to fill the unevenness of the thin film transistor 13 and the light reflection layer 8. A base alignment layer 22 is formed on the flattening layer 21 and is used to uniaxially align a polymer liquid crystal formed thereon. The pixel electrode 11 is electrically connected to the corresponding drain electrode 20 of the thin film transistor 13 via a contact hole 23 provided through the quarter-wave plate layer 9 and the planarizing layer 21.

FIG. 2 is a graph showing the solvent resistance of the liquid crystal polymer constituting the quarter-wave plate layer. The vertical axis shows the rate of change of the retardation, and the horizontal axis shows the temperature. The retardation is an amount determined by the product of the thickness of the quarter-wave plate layer and the refractive index anisotropy, and is an index indicating the polarization conversion function of the quarter-wave plate layer. It can be said that the smaller the change in retardation, the more resistant the solvent is. The temperature on the horizontal axis is the processing temperature when forming the alignment layer on the quarter-wave plate layer. Specifically, vacuum drying is performed after the alignment agent is applied by spin coating or the like, and the drying temperature at that time is indicated. Vacuum drying can evaporate the solvent at a lower temperature than ordinary air drying, and is effective for maintaining the uniaxial orientation of the polymer liquid crystal. In this graph, an alignment layer is formed by using three types of alignment agents and changing the vacuum drying temperature between 20 ° C. and 70 ° C. respectively. After forming the alignment layer, the retardation of the quarter-wave plate layer was measured, and the effect of the solvent contained in the alignment agent at the coating stage was examined. The mark ● indicates an aligning agent obtained by dissolving polyamic acid in NMP and further diluting 1: 9 with BC. The mark (3) indicates that the aligning agent obtained by dissolving the polyamic acid in DMTG according to the present invention was further diluted 3:17 with BC. The symbol も also indicates an aligning agent obtained by dissolving the polyamic acid in DMTG according to the present invention and further diluting 3:17 with DEDG. As is clear from the graph, the retardation changes and the polymer liquid crystal dissolves when the vacuum drying temperature exceeds 35 ° C with respect to NMP conventionally used as a solvent for the vertical alignment agent such as polyamic acid. Would. On the other hand, when DMTG is used as the main solvent of the vertical alignment agent such as polyamic acid, the retardation of the polymer liquid crystal does not change even when the vacuum drying temperature is increased to about 55 ° C. Thus, instead of NMP, D
By using MTG, damage to the polymer liquid crystal is suppressed, and the yield in the spin coating or vacuum drying process is improved. By using DMTG, the dissolution of the polymer liquid crystal does not occur, and it is possible to prevent a decrease in contrast of the display device. From the viewpoint of manufacturing efficiency, the vacuum drying temperature can be increased to about 55 ° C. as compared with the conventional case, and the vacuum drying time can be shortened accordingly.
Also, as is clear from the graph, butyl cellosolve (BC) is sufficiently effective as a diluting solvent, but diethylene glycol diethyl ether (DEDG) is more effective.

Generally, a polyimide-based polymer is synthesized according to the reaction formula shown in FIG. That is, the diamine compound and the acid anhydride shown in (A) are reacted in a solvent to obtain (B)
The following polyamic acid is synthesized. The alignment agent used in the present invention is a solution of this polyamic acid. The diamine compound and the acid anhydride are reacted in a solvent composed of DMTG. When the polyamic acid is further heated, it is dehydrated and ring-closed,
The polyimide shown in (C) is obtained. This polyimide can also be used as a vertical alignment agent, in which case DMTG is used as the solvent according to the present invention. Where R ₁ and R
_Since the structure of the portion represented by ₂ greatly affects the properties of polyamic acid or polyimide used as an aligning agent, when used as a vertical alignment agent for nematic liquid crystal, it is necessary to select a molecular structure matching this. . As described above, the present invention uses a solution of, for example, polyamic acid as the polyimide-based organic alignment agent.
DMTG is used as a main solvent, but a diluent having a low surface tension, such as BC or DEDG, is mixed and used to improve coating properties. Polyamic acid has good solubility in DMTG, and it is easy to adjust the concentration and viscosity as a coating agent. Basically, a polyimide-based organic alignment film having a composition capable of vertically aligning liquid crystal molecules is selected. Furthermore,
By rubbing the surface, when the liquid crystal molecules shift from vertical alignment to horizontal alignment in response to voltage application, it is possible to regulate the tilt direction in the rubbing direction.

FIG. 4 is a schematic view showing the chemical structure of a side-chain type polymer liquid crystal used for a quarter-wave plate layer. (I) shows a polymer liquid crystal having biphenylbenzoate as a pendant entering a side chain. That is, side chains are bonded to the alkyl main chain at predetermined intervals (only one side chain is shown in the figure). The space length of this side chain is 6 in carbon number, but the present invention is not limited to this. Biphenyl benzoate is attached to the tip of this side chain as a pendant. (II) represents a side chain type polymer liquid crystal having methoxybiphenyl in addition to biphenylbenzoate as a pendant. The space length of the side chain to which methoxybiphenyl is bonded is 2 in carbon number, but the present invention is not limited to this. (III)
Shows a side chain type polymer liquid crystal having methoxyphenyl benzoate as a pendant. The side chain has a space length of 2 or 6 carbon atoms bonded to the main chain.
Types (I) and (II) have better solvent resistance than type (III). Therefore, when an organic alignment layer such as polyamic acid is formed on a quarter-wave plate layer, a quarter-wavelength liquid crystal having excellent solvent resistance (I) and (II) is used in advance. It is preferable to form a one-wavelength plate layer. That is, it is preferable to form a quarter-wave plate layer by forming a polymer liquid crystal in which biphenylbenzoate is introduced into a side chain separated from the alkyl main chain.

Finally, a method of manufacturing the reflective guest-host liquid crystal display device shown in FIG. 1 will be described in detail with reference to FIGS. First, in the step (A) of FIG. 5, a thin film transistor 13 is integratedly formed on an insulating substrate 2 made of glass, quartz, or the like. Specifically, after the gate electrode 14 made of a refractory metal film or the like is formed by patterning,
A gate oxide film 15 is formed by depositing a silicon oxide film or a silicon nitride film by CVD or the like. A semiconductor thin film 16 made of polycrystalline silicon or the like is formed thereon, and is patterned in an island shape according to the element region of the thin film transistor 13. A stopper 17 is provided thereon so as to match the gate electrode 14. Using the stopper 17 as a mask, an impurity is implanted into the semiconductor thin film 16 by ion doping or ion implantation to form a bottom-gate thin film transistor 13. This thin film transistor 13 is referred to as P
It is covered with an interlayer insulating film 18 made of SG or the like.

In step (B), after opening a contact hole in the interlayer insulating film 18, aluminum or the like is sputtered and patterned into a predetermined shape to form a source electrode 19
And a drain electrode 20. At this time, the light reflection layer 8 is formed at the same time. In the region where the light reflection layer 8 is to be formed, irregularities are formed in advance as a base. As a result, the light reflection layer 8 has light scattering properties, and a so-called white paper display appearance is obtained. Further, a flattening layer 21 made of an acrylic resin or the like is formed so as to fill the unevenness of the thin film transistor 13 and the light reflection layer 8. in addition,
A rubbing treatment is performed by applying a polyimide resin, and a base alignment layer 22 is provided. A quarter-wave plate layer 9 made of a uniaxially oriented polymer liquid crystal is formed thereon. In particular,
A polymer liquid crystal is formed on the base alignment layer 22 with a predetermined thickness. The polymer liquid crystal is a material capable of performing a phase transition between a nematic liquid crystal phase on the high temperature side and a glass solid phase on the low temperature side at a predetermined transition point. For example, the polymer liquid crystal is in a glassy state at room temperature, and is preferably a main chain type or a side chain type having a phase transition point at 100 ° C. or higher. This polymer liquid crystal is a transparent substance having no optical absorption in the visible region. After the polymer liquid crystal is dissolved in an organic solvent, it is applied to the surface of the base alignment layer 22 by spin coating. In addition,
Instead of spin coating, application may be performed using dipping or screen printing. When spin coating is performed, conditions such as the concentration of the solution and the number of spin rotations are appropriately set so that the film thickness causes a phase difference of λ / 4 in the visible light region. Here, λ represents the wavelength of the incident light. Thereafter, the substrate 2 is once heated to a temperature equal to or higher than the transition point and then cooled to room temperature equal to or lower than the transition point. 9 is formed.

In step (C), a photoresist 10 is applied so as to cover the entire surface of the quarter-wave plate layer 9. As a coating method, spin coating or screen printing can be used. Proceeding to the step (D), the photoresist 10 is exposed and developed, and a window 10a is provided in a region that is aligned with the lower drain electrode 20.

In step (E) of FIG. 6, etching is performed using the patterned photoresist 10 as a mask, and a quarter-wave plate layer 9, a base alignment layer 22, and a planarizing layer 2 are formed.
1 is opened. Here, dry etching in which oxygen plasma or the like is applied is employed. Proceeding to step (F), after removing the used photoresist 10, the IT is placed on the quarter-wave plate layer 9.
A transparent conductive film made of O or the like is formed, patterned into a predetermined shape, and processed into the pixel electrode 11. This pixel electrode 11
Is the thin film transistor 13 through the contact hole 23
Is electrically connected to the drain electrode 20.

Finally, proceeding to step (G), an organic alignment layer 12 is formed on the pixel electrode 11 and the quarter-wave plate layer 9. That is, a vertical alignment agent is continuously applied on the pixel electrode 11 and the quarter-wave plate layer 9 exposed between the pixel electrodes 11 and rubbed to form the alignment layer 12. This alignment agent is, for example, a liquid in which polyamic acid is dissolved in DMTG as a solvent. A polyamic acid or polyimide is dissolved in triethylene glycol dimethyl ether, and a vertical alignment agent diluted with diethylene glycol diethyl ether is applied by, for example, spin coating. After coating, vacuum drying is performed in a temperature range of 35 ° C. to 55 ° C. to form an alignment layer 12. For example, if vacuum drying is performed at 45 ° C. for 1 hour, most of the solvent contained in the vertical alignment agent is removed. Further, air drying is performed at 90 ° C. for about one hour to completely solidify the vertical alignment agent. Thereafter, the organic alignment layer 12 is rubbed in a certain direction with a buff material wound around a rotating roller to impart an alignment ability to liquid crystal molecules. Finally, although not shown, the upper substrate on which the counter electrode and the alignment layer are formed in advance is bonded to the lower substrate 2 via a predetermined gap, and the guest-host liquid crystal containing the dichroic dye is filled in this gap. After the injection, the reflective guest-host liquid crystal display device is completed.

[0019]

As described above, according to the present invention,
The quarter-wave plate layer is composed of a uniaxially oriented polymer liquid crystal film having relatively poor solvent resistance, while the alignment layer is composed of an organic coating film rubbed by applying a vertical alignment agent. At this time, a vertical alignment agent using triethylene glycol dimethyl ether as a solvent is used. Thereby, the quarter-wave plate layer is not damaged, and its optical function can be stably maintained. As a result, the orientation of the guest-host liquid crystal can be freely controlled, stable vertical alignment can be realized, and this greatly contributes to improvement in contrast.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing a basic configuration of a reflective guest-host liquid crystal display device manufactured according to the present invention.

FIG. 2 is a graph showing the solvent resistance of a quarter-wave plate layer.

FIG. 3 is a schematic diagram showing the composition of a vertical alignment agent.

FIG. 4 is a schematic diagram showing a composition of a polymer liquid crystal.

FIG. 5 is a process chart showing a method of manufacturing the reflective guest-host liquid crystal display device shown in FIG.

FIG. 6 is a process drawing showing the same manufacturing method.

FIG. 7 is a cross-sectional view illustrating an example of a conventional reflective guest-host liquid crystal display device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Substrate, 3 ... Guest host liquid crystal, 4 ... Liquid crystal molecule, 5 ... Dichroic dye, 6 ...
Counter electrode, 7 ... orientation layer, 8 ... light reflection layer, 9 ...
A quarter-wave plate layer, 11 ... pixel electrodes, 12 ...
Alignment layer, 13 thin film transistor, 20 drain electrode, 21 flattening layer, 22 base alignment layer, 23 contact hole

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G09F 9/35 385 G09F 9/35 385

Claims (5)

[Claims] 1. A first step of forming a light reflection layer on a first substrate, and a second step of forming a quarter-wave plate layer made of uniaxially oriented polymer liquid crystal on the light reflection layer. A third step of forming an electrode on the quarter-wave plate layer, and using triethylene glycol dimethyl ether as a solvent on the electrode and on the quarter-wave plate layer exposed between the electrodes. A fourth step of applying a vertical alignment agent to form an alignment layer, a fifth step of bonding a second substrate on which electrodes are formed in advance to the first substrate via a predetermined gap, Performing a sixth step of injecting a guest-host liquid crystal containing a reactive dye into the gap. 2. The method of manufacturing a reflective guest-host liquid crystal display device according to claim 1, wherein in the fourth step, a vertical alignment agent obtained by dissolving polyamic acid or polyimide in triethylene glycol dimethyl ether is applied. 3. The method of manufacturing a reflective guest-host liquid crystal display device according to claim 2, wherein in the fourth step, the vertical alignment agent is applied in a state diluted with diethylene glycol diethyl ether. 4. The reflection-type guest-host liquid crystal display device according to claim 1, wherein in the fourth step, an alignment layer is formed by applying a vertical alignment agent and performing vacuum drying in a temperature range of 35 ° C. to 55 ° C. Manufacturing method. 5. The reflection according to claim 1, wherein in the second step, a quarter-wave plate layer is formed by depositing a polymer liquid crystal in which biphenylbenzoate is introduced into a side chain separated from an alkyl main chain. Manufacturing method of a liquid-crystal guest-host liquid crystal display device.