JP2002267829A - Color filter, method for manufacturing the same and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter with high resolution at a low cost and to provide the color filter manufactured by the method and a liquid crystal display device with the color filter built therein. SOLUTION: The method for manufacturing the color filter comprises at least a step to form a liquid crystal layer containing at least a liquid crystalline compound having at least one polymerizable group and a photo-reactive chiral agent, a step to apply light in a photosensitive wavelength region of the photo- reactive chiral agent in the layer to the layer in a picture shape and a step to photo polymerize the liquid crystalline compound having at least one polymerizable group. The method for manufacturing the color filter, the color filter and the liquid crystal display device are characterized by subjecting the liquid crystal layer to transparentizing treatment prior to the step to apply the light in the photosensitive wavelength region of the photo-reactive chiral to the layer in the picture shape.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter, a color filter produced by the method, and a liquid crystal display device incorporating the color filter.

[0002]

2. Description of the Related Art In addition to portable information terminals, personal computers, word processors, amusement devices, television devices, and the like, color filters have been increasingly used in various electronic devices and display panels for electric devices. Conventionally, a display device using a liquid crystal is incorporated in these devices, but this display device has an advantage of low power consumption and thinness. These display devices are broadly divided into a transmission type display device having a backlight light source and a reflection type display device of a front light type having no light source or using a light guide plate on the entire surface. , Color filters are used. For example, a color filter used for a color liquid crystal display or the like generally includes red (R), green (G), and blue (B) pixels, and a black matrix for improving display contrast is formed between the pixels. It is composed.

[0003] Such a color filter router has conventionally been
What is manufactured using a pigment dispersion method or a dyeing method is the mainstream. The pigment dispersion method is a method in which a pigment is dispersed in a photoresist and applied to a substrate glass to perform a pattern exposure / development step, and is a method excellent in patterning edge, resolution, film uniformity, and the like. However, there are problems such as the necessity of a photoresist process and the fact that color adjustment cannot be performed as easily as using a dye because a pigment is used. In addition, when a photoresist is applied on a substrate by using the spin coating method, there are disadvantages in that the material loss is large and the application unevenness when applying the photoresist on a large-area substrate is large. The dyeing method is a method of dyeing a transparent resin pattern obtained by imparting photosensitivity to gelatin or the like later.The light transmittance is high based on the transparency of the dye, and the chromaticity is adjusted by abundant types of the dye. Although it has the feature of being easy, it requires a drawback that the number of steps such as a photoresist step is larger than that of the pigment dispersion method.

[0004] In addition, as a method for producing a color filter, a printing method, an electrodeposition method, an ink jet method, and the like are known. Since the printing method is a method of sequentially printing each color one by one, it is difficult to align a pattern of each color,
Although the resolution of the pixels is low and the film thickness is not uniform, it is difficult to form a high-definition image pattern. However, the utilization rate of the material is high. According to the electrodeposition method,
Although it is possible to obtain a color filter having relatively high resolution and little unevenness of the colored layer, it has a disadvantage that the manufacturing process is complicated and liquid management is difficult. In the case of the ink jet method, there are problems of resolution and color mixing between adjacent pixels.

The above color filters are light absorption type color filters, and can transmit only about 1/3 of the light from the light source in principle. Therefore, it cannot be said that the brightness is sufficient. To compensate for this drawback, for example, in the case of a transmissive display device, it is conceivable to increase the brightness of the backlight. However, there is a problem that the power consumption increases and the advantages of the liquid crystal display device are impaired.

To solve these problems, US Pat.
No. 614 proposes a color filter using a cholesteric polarizer which does not require a liquid developing step. Cholesteric polarizers selectively reflect circularly polarized light of a specific wavelength,
Since it has the property of transmitting circularly polarized light having a wavelength other than this, unlike the color filters made of the colored resin, the utilization efficiency can be increased by reusing the transmitted light, and a substantially bright color filter Can be formed. Therefore, this type of color filter is suitable for a reflection type liquid crystal display. Further, since a pattern having different selective reflection wavelengths can be formed in the same layer without the need for a developing step, it is advantageous in terms of cost. In this patent, a chiral agent that isomerizes from chiral to achiral is used as a chiral agent, but in order to prevent diffusion of the isomerized chiral agent and increase resolution, a polymerizable material is added to the liquid crystal in advance. Then, it is said that it is effective to form a polymer network between pixels. However, in order to form a polymer network between pixels, a step of polymerizing between pixels by exposure is added, which is not sufficient from the viewpoint of cost reduction, and a liquid crystal contains a polymerizable material. This leads to non-uniform alignment of the liquid crystal.

In the color filter disclosed in JP-A-10-282324, a light absorbing layer is provided on a substrate, a concave portion is provided in the light absorbing layer, and the helical pitch of the liquid crystal phase has a high temperature dependency in the concave portion. A UV-curable cholesteric liquid crystal or chiral nematic liquid crystal layer is provided, and light is radiated at different heating temperatures for each pixel to obtain selective reflection of red, blue, and green. It is formed to prevent exposure fog due to irregular reflection in the liquid crystal layer at the time of exposure. However, since a complicated process is required, sufficient cost reduction cannot be achieved. Further, Japanese Patent Application Laid-Open
JP-A-95883 discloses a method for producing a reflective film in which a selective reflection wavelength is changed by adding a non-photoreactive chiral agent to a polymerizable liquid crystal compound and changing the photopolymerization rate depending on the amount of light irradiation for each pixel. Although this method does not cause diffusion of the chiral agent, it is difficult to sufficiently control the photopolymerization rate by the light irradiation amount.

On the other hand, as a color filter using a photoreactive chiral agent, Japanese Patent Application Laid-Open No. 2000-154168 discloses a crosslinked liquid crystal composition containing a specific high molecular weight acrylic photoisomerized chiral compound and a liquid crystal polymer. In this liquid crystal composition, the chiral agent has a high molecular weight, so that diffusion is unlikely to occur, but there is a disadvantage that it takes time to reorient the liquid crystal.

On the other hand, the present applicant has previously formed a color filter layer by spraying an ink containing a polymerizable liquid crystal compound by an ink jet method as a color filter utilizing such selective reflection of a cholesteric liquid crystal phase. A method was filed (Japanese Patent Application No. 11-343666).

The present applicant has further filed an application for a method of forming a color filter by irradiating light to a layer containing a photoreactive chiral agent having a specific structure in a polymerizable liquid crystalline compound (Japanese Patent Application No. 2000-193142, Japanese Patent Application No. 2000-193143). The photoreactive chiral agent has a chiral site and a site that undergoes a structural change due to light irradiation. For example, the photoreactive chiral agent greatly changes the twisting power (HTP) of the helical structure of the liquid crystal in accordance with the amount of irradiation. , Green (G) and red (R).

In the production of a color filter as described above, first, a polymerizable liquid crystal compound and a photoreactive chiral agent or a liquid crystal layer containing a polymerizable monomer or the like is irradiated with light to form a photoreactive liquid crystal compound. Although the chiral agent causes photoisomerization or the like, the liquid crystal layer is easily clouded, and it is difficult to form a transparent liquid crystal layer. If the liquid crystal layer is not transparent and is cloudy, light scattering occurs in the liquid crystal layer, and it is impossible to form an accurate pattern without bleeding according to the exposure mask, which leads to a decrease in resolution. Problems arise.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a high-resolution color filter at low cost. An object of the present invention is to provide a color filter manufactured by the above method and a liquid crystal display device incorporating the color filter.

[0013]

The above objects can be attained by providing the following color filter manufacturing method, color filter, and liquid crystal display device. (1) A step of forming a liquid crystal layer containing at least a liquid crystalline compound having at least one polymerizable group and a photoreactive chiral agent, wherein light in the photosensitive wavelength region of the photoreactive chiral agent of the liquid crystal layer is image-wise formed. Irradiating the liquid crystal compound having at least one polymerizable group with a photopolymerizable compound, at least a step of photopolymerizing the liquid crystal compound having at least one polymerizable group, wherein the light in the photosensitive wavelength region of the photoreactive chiral agent. A method for producing a color filter, wherein a transparentizing treatment is performed on the liquid crystal layer prior to the step of imagewise irradiation. (2) The above (1), wherein the transparentizing treatment includes a step of heating the liquid crystal layer and a subsequent quenching step.
3. The method for producing a color filter according to item 1.

(3) The method for producing a color filter as described in (1) or (2) above, wherein the heating is performed in a temperature range in which the liquid crystal compound exhibits a nematic phase state. (4) The method for producing a color filter according to any one of (1) to (3), wherein the step of photopolymerizing is performed at normal temperature. (5) The method for producing a color filter according to any one of (1) to (4), wherein the liquid crystal layer further contains a photopolymerization initiator. (6) A color filter produced by the method for producing a color filter according to any one of (1) to (5). (7) In a liquid crystal display device including at least one color filter, a liquid crystal layer, and a liquid crystal drive electrode between a pair of substrates that are light-transmissive, the color filter is the color filter according to (6). A liquid crystal display device, comprising:

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a method for manufacturing a color filter of the present invention will be described. The method for producing a color filter of the present invention comprises the steps of:
Forming a liquid crystal layer containing a liquid crystalline compound having one and a photoreactive chiral agent, irradiating light in the photosensitive wavelength range of the photoreactive chiral agent of the liquid crystal layer imagewise, at least the polymerizable group At least a step of photopolymerizing a liquid crystal compound having one, wherein the liquid crystal layer is formed prior to the step of irradiating light in the photosensitive wavelength region of the photoreactive chiral agent in an imagewise manner. On the other hand, transparent processing is performed. In the method of manufacturing a color filter according to the present invention, a color filter having a high resolution can be obtained by the transparency processing. Further, the method for manufacturing a color filter of the present invention does not use a photolithography method which causes an increase in cost, so that a color filter can be manufactured at low cost. Further, in the method for producing a color filter, a step of imagewise irradiating light in the photosensitive wavelength region of the photoreactive chiral agent of the liquid crystal layer and a step of photopolymerizing a liquid crystalline compound having at least one polymerizable group. Usually, the temperature of the liquid crystal layer during photopolymerization is performed within the nematic phase temperature,
When the temperature is lower than this temperature, selective reflection does not occur, but it was confirmed that selective reflection occurs even when photopolymerization is performed at room temperature by performing the above-described transparentizing treatment. Therefore, the method for producing a color filter of the present invention is advantageous in terms of cost because the heating step is omitted.

[Liquid Crystal Composition] In the method for producing a color filter of the present invention, a liquid crystal composition used for forming a liquid crystal layer on a substrate is at least a liquid crystal compound having at least one polymerizable group and a photoreactive compound. A chiral agent. Further, it is preferable to further add a polymerization initiator to the liquid crystal composition.

In the liquid crystal composition, the low molecular weight liquid crystal compound having a polymerizable group is preferably a nematic liquid crystal compound having a polymerizable group. The polymerizable group of the liquid crystal compound secures sufficient curability and improves the heat resistance of the layer.

Specific examples of the low-molecular liquid crystal compound having a polymerizable group include the following compounds. However, the present invention is not limited to these.

[0019]

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[0020]

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[0021]

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In the above formula, n represents an integer of 1 to 1000. In each of the above exemplified compounds, those in which the connecting group of the aromatic ring is changed to the following structure can also be mentioned as suitable compounds.

[0023]

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The content of the liquid crystal compound is preferably from 30 to 99.9% by mass, more preferably from 50 to 95% by mass, based on the mass of the solid content of the liquid crystal composition. When the content is less than 30% by mass, the orientation is insufficient and a desired selective reflection color may not be obtained.

(Photoreactive Chiral Agent) Next, the photoreactive chiral agent will be described. The photoreactive chiral agent has a chiral site and a photoreactive site that undergoes a structural change upon irradiation with light,
For example, the torsional force (H
TP). In order to increase the helical structure inducing force by light irradiation, it is preferable that the degree of structural change by light irradiation is large. Further, as the photoreactive chiral agent, those having a solubility parameter SP value close to that of a liquid crystalline compound are desirable. Further, when the photoreactive chiral agent has a structure in which one or more polymerizable bonding groups are introduced into the molecule, the heat resistance of the liquid crystal phase is improved.

Examples of photoreactive sites whose structure is changed by light irradiation include photochromic compounds (Kingo Uchida, Masahiro Irie, Chemical Industries, vol. 64, 640p, 1999,
Kingo Uchida, Masahiro Irie, Fine Chemical, vol. 28
(9), 15p, 1999).
Further, the structural change means a decomposition or addition reaction, isomerization, dimerization reaction, or the like caused by light irradiation on a photoreactive site, and the structural change may be irreversible. Examples of the chiral moiety include, for example, Hiroyuki Nohira, Chemical Review, N
o. The asymmetric carbon described in 22 Chemistry of Liquid Crystals, 73p: 1994, and the like correspond thereto.

Examples of the photoreactive chiral agent used in the present invention include, for example, Japanese Patent Application No. Hei 11
-343666, paragraphs [0044] to [004]
7], a photoreactive chiral agent described in Japanese Patent Application No. 2000-193.
In addition to the photoreactive chiral agents described in paragraphs [0021] to [0029] of No. 142, Japanese Patent Application No. 2000-380919.
Nos. Paragraphs [0019] to [0043], paragraphs [002] of Japanese Patent Application No. 2000-381001.
0] to [0044];
Nos. 00-381002, paragraphs [0016] to [004]
0], Japanese Patent Application 2000-3810
No. 03, paragraphs [0015] to [0036], and optically active compounds described in Japanese Patent Application No. 2000-381966, paragraph [0].
017] to [0050], paragraphs [0018] to [00] of Japanese Patent Application No. 2000-381967.
44], Japanese Patent Application No. 2000-382.
The optically active compounds described in paragraphs [0020] to [0049] of No. 515 can be used as a photoreactive chiral agent.

In the liquid crystal composition of the present invention, in addition to the low molecular weight liquid crystal compound having a polymerizable group and the photoreactive chiral agent, a polymerizable monomer, a polymerization initiator, a binder resin, a solvent, , Surfactants, polymerization inhibitors, thickeners,
Other components such as dyes, pigments, ultraviolet absorbers, and gelling agents can be included. In the liquid crystal composition of the present invention, it is particularly preferable to use a surfactant in combination. For example, when applying a liquid crystal composition in the form of a coating liquid to form a layer, the alignment state at the air interface of the layer surface can be controlled three-dimensionally, and in particular, in the case of a cholesteric liquid crystal phase, a selective reflection wavelength having higher color purity can be obtained. Obtainable. (Polymerizable monomer) A polymerizable monomer may be used in the liquid crystal composition of the present invention. When the polymerizable monomer is used in combination, the distribution of the selective reflection wavelength is formed (patterned) by changing the torsional force of the liquid crystal by light irradiation, and then the helical structure (selective reflectivity) is fixed, and the liquid crystal composition after fixing is fixed. The strength of the object can be further improved. However, when the liquid crystal compound has an unsaturated bond in the same molecule, it is not always necessary to add.

The polymerizable monomer includes, for example, a monomer having an ethylenically unsaturated bond. Specifically, in addition to a polyfunctional monomer such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, Compounds shown can be mentioned,
However, the present invention is not limited to these.

[0030]

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The amount of the polymerizable monomer to be added is preferably 0.5 to 50% by mass based on the mass of the solid content of the liquid crystal composition. When the addition amount is less than 0.5% by mass,
In some cases, sufficient curability cannot be obtained, and when it exceeds 50% by mass, the alignment of liquid crystal molecules is hindered, and sufficient color formation may not be obtained.

(Photopolymerization Initiator) In order to fix the helical structure after changing the twisting force of the liquid crystal by light irradiation and to further improve the strength of the liquid crystal composition after the fixation, polymerization with a polymerizable liquid crystal compound is performed. When utilizing a reaction, it is preferable to add a photopolymerization initiator. Further, the photosensitive wavelength region of the photopolymerization initiator is preferably different from the photosensitive wavelength region of the photoreactive chiral agent. Here, having different photosensitive wavelengths means that both photosensitive central wavelengths do not overlap. When the photosensitive wavelength region of the photoreactive chiral agent is different from the photosensitive wavelength region of the photopolymerization initiator, the irradiation of light for changing HTP and the irradiation of light for photopolymerization do not affect each other. Therefore, when imagewise exposed to change the HTP, photopolymerization does not proceed, so that patterning with the HTP change rate as set becomes possible, while photopolymerization to fix the helical structure is performed. Indicates that the photoreactive chiral agent does not react to light and the HT formed
The P change pattern can be reliably fixed, and selective reflection according to the setting is achieved.

The photopolymerization initiator can be appropriately selected from known ones, for example, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxy) (Styryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethylketal, thioxanthone / Amines and triarylsulfonium hexafluorophosphate. In addition, bisacylphosphine oxides such as bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide described in JP-A-10-29997 and the like, and DE4 such as Lucirin TPO and the like.
Acylphosphine oxides described in JP 230555 and the like.

The addition amount of the photopolymerization initiator is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 5% by mass, based on the solid content of the liquid crystal composition. If the amount is less than 0.1% by mass, the curing efficiency at the time of light irradiation is low, so that it may take a long time. If the amount exceeds 20% by mass, the light transmittance from the ultraviolet region to the visible light region may be required. May be inferior.

[Production of Color Filter] The color filter of the present invention can be produced from the above-mentioned liquid crystal composition. The color filter of the present invention may be in the form of a sheet in which the color filter layer is composed of only the liquid crystal composition, or in a mode in which the color filter layer is provided on a desired support or substrate. And other layers such as an alignment film and a protective film may be provided. Two or more liquid crystal layers can be stacked.

The method for producing the color filter is not particularly limited, and at least the step of forming a liquid crystal layer on the color filter substrate and the image formation of light in the photosensitive wavelength region of the photoreactive chiral agent of the liquid crystal layer are performed. Irradiating and photopolymerizing the liquid crystalline compound having at least one polymerizable group. In addition, in addition to the above-described steps, the step of producing the color filter of the present invention may include a step of subjecting the contact surface between the liquid crystal layer and the color filter substrate or the temporary support to an alignment treatment as described below. .

The liquid crystal layer may be formed by directly applying the liquid crystal composition of the present invention to a color filter substrate, or by peeling the liquid crystal layer once formed on the temporary support into close contact with the color filter substrate and then removing the temporary support. This is performed by a transfer method.

When the photoreactive chiral agent used in the present invention is irradiated with light in the photosensitive wavelength range, a photoreaction (isomerization, decomposition, addition, dimerization, etc.) occurs according to the amount of light, and as a result, the liquid crystal Change the pitch of the spiral structure. Therefore, if the light irradiation intensity is changed for each desired region of the liquid crystal layer and light irradiation is performed, a change in the pitch of the helical structure occurs in accordance with the irradiation intensity, and selective reflection of light having a wavelength corresponding to the pitch occurs. Presents multiple colors. In order to irradiate different light amounts to different regions, for example, a method of exposing through an exposure mask manufactured by changing the light transmittance imagewise is preferably used. In this method, the degree of photoreaction differs imagewise by a single light irradiation (as a result, the helical pitch of the liquid crystal phase can be changed imagewise).
This is a preferable method because a liquid crystal layer can be formed.

In the present invention, prior to this step,
The liquid crystal layer is subjected to a transparency treatment. In the transparency treatment, for example, a transparent solid liquid crystal film can be obtained by heating the liquid crystal layer to a temperature equal to or higher than the nematic phase transition temperature or equal to or higher than the isotropic temperature, and then rapidly cooling the liquid crystal layer. Quenching
The liquid crystal layer after cooling is cooled from a temperature higher than the nematic phase transition temperature or higher than the isotropic temperature to, for example, room temperature, at a cooling rate large enough to maintain at least transparency of the cooled liquid crystal layer. Next, as described above, the liquid crystal layer is exposed to light having different irradiation intensities in a pattern, so that different regions have different sizes of photoreactions. At the time of light irradiation for causing a photoreaction to the photoreactive chiral agent, if the liquid crystal layer is not transparent and is opaque, light scattering occurs in the liquid crystal layer and there is no accurate bleeding according to the exposure mask. Although a pattern cannot be formed, which leads to a decrease in resolution, in the present invention, such a transparentizing process is performed, so that a color filter having a high resolution can be obtained.

Another feature of the production of the color filter of the present invention is that selective reflection is already exhibited after the exposure. Therefore, in the conventional method, after the exposure, unless the liquid crystal layer is heated to a nematic phase temperature, selective reflection does not occur, so that it is necessary to heat the liquid crystal layer to the point N prior to photopolymerization, In the color filter of the present invention, such a heat treatment is not necessarily required.

However, as usual, the liquid crystal layer is heated to the nematic phase temperature or, before being heated to the nematic phase temperature, once heated to the isotropic temperature and then cooled to reach the nematic phase temperature. Alternatively, it is also possible to irradiate the entire surface of the liquid crystal layer with light for photopolymerization (curing). In the present invention, it is preferable to perform photopolymerization at room temperature from the viewpoint that the heat treatment can be omitted, but from the viewpoint of uniformity of the alignment state, it is preferable to perform photopolymerization at a temperature at which the liquid crystal layer maintains a nematic phase. .

As described above, the wavelength region of light that causes a photoreaction with the photoreactive chiral agent (the photosensitive wavelength range of the photoreactive chiral agent) and the wavelength region of light that is photopolymerized (when a polymerization initiator is used) , Their photosensitive wavelength ranges) are different.

The wavelength of the light that causes the photoreactive chiral agent to undergo a photoreaction may be set in the light-sensitive wavelength region of the photoreactive chiral agent, particularly a wavelength close to the light-sensitive peak wavelength, so that sufficient patterning sensitivity can be obtained. It is preferable in that it can be obtained. Also,
The wavelength of the light to be photopolymerized is preferably set to a light sensitive wavelength range of the polymerization initiator, particularly to a wavelength close to the light sensitive peak wavelength, in that sufficient photopolymerization sensitivity can be obtained. The irradiation intensity of these lights can be appropriately selected so as to obtain sufficient light sensitivity.

The following is a more specific description. [First Embodiment] The first embodiment is a method using a transfer method for forming a liquid crystal layer on a color filter substrate. (1) A step of providing a layer of the liquid crystal composition of the present invention on a temporary support to form a transfer material having at least a liquid crystal layer. The liquid crystal layer is formed by applying the liquid crystal composition of the present invention to a temporary support using a bar coater, a spin coater, or the like. Between the liquid crystal layer and the temporary support, a thermoplastic resin (acrylic resin, polyester, urethane resin, or the like) is used from the viewpoint of ensuring adhesion during transfer, such as when there is a foreign substance or the like on the transfer target. It is also possible to provide a cushion layer. In addition, it is preferable to perform an alignment treatment (formation of an alignment film and a rubbing treatment) on the surface of the temporary support or the cushion layer. Further, a cover film for protection can be provided on the liquid crystal layer. (2) a step of laminating the transfer material on a light transmissive substrate; The substrate may be provided with an image receiving layer. Also,
It is preferable to perform the same alignment treatment as in the above (1) on the substrate or the image receiving layer. (3) A step of transferring the liquid crystal layer to the light transmitting substrate and peeling off the temporary support (transfer step). After passing through the following (4), a plurality of liquid crystal layers can be formed by further stacking transfer materials in the same manner. (4) A step of irradiating the liquid crystal layer imagewise with light through an exposure mask to form a pixel pattern showing a selective reflection color, and further irradiating light to cure the liquid crystal layer (exposure step). In the present invention, the liquid crystal layer is subjected to the above-described transparency treatment before the image is irradiated with light.

Hereinafter, a method of manufacturing the color filter according to the first embodiment will be described with reference to the drawings. First, FIG.
As shown in (A), a cushion layer 12 is provided on a temporary support 10, and an orientation film 14 such as polyvinyl alcohol is further provided.
Are laminated. Next, as shown in FIG. 1B, a rubbing process is performed on the alignment film. This rubbing treatment is not always necessary, but the rubbing treatment can further improve the orientation. Next, as shown in FIG. 1C, a liquid crystal composition is applied on the alignment film 14 and dried to form a liquid crystal layer 16, and then a cover film 18 is provided on the liquid crystal layer 16, A transfer material 20 is prepared.

On the other hand, as shown in FIG. 1- (D), an alignment film 24 is formed on another substrate 22 in the same manner as in FIG. 1- (B), and its surface is subjected to a rubbing treatment. Hereinafter, this is referred to as a color filter substrate 26. Next, after peeling off the cover film 18 of the transfer sheet material 20, FIG.
As shown in (E), the surface of the liquid crystal layer 16 of the transfer sheet 20 and the surface of the alignment film 24 of the color filter substrate 26 are overlapped so as to be in contact with each other, and passed through a roll rotating in the direction of the arrow in the figure. Laminated. Then, FIG.
As shown in (F), the liquid crystal layer 16 is transferred together with the alignment film 14 onto the color filter substrate 26 by being peeled off between the alignment film 14 of the transfer material 20 and the cushion layer 12. In this case, the cushion layer 12 does not necessarily have to be peeled off together with the temporary support 10.

After the transfer, the liquid crystal layer is subjected to the above-described transparency treatment, and as shown in FIG. 3G, an exposure mask having a plurality of regions having different light transmittances above the alignment film 14. 28 and bandpass filter (not shown)
Is arranged, and ultraviolet rays are irradiated through the mask 28 to cause a photoreaction to the photoreactive chiral agent.

Next, as shown in FIG. 3 (H), the same light source as in the above step (G) (without using a band-pass filter) is applied to the liquid crystal layer 16 to form the liquid crystal layer 16 (G). The pattern is fixed by irradiating ultraviolet rays with an irradiation intensity different from that of the light irradiation of the above). Thereafter, unnecessary portions on the liquid crystal layer 16 (for example, remaining portions such as a cushion layer and an intermediate layer, and unexposed portions) are removed using 2-butanone, chloroform, or the like, so as to be illustrated in FIG. Like BG
A liquid crystal layer having an R reflection region can be formed.

[Second Aspect] The second aspect is a method of forming a liquid crystal layer directly on a substrate constituting a color filter. This is a method in which the same transparency processing and exposure step as in the above are performed.

The thickness of the liquid crystal layer functioning as a color filter is preferably 1.5 to 4 μm.

Regarding these steps and the materials to be used, such as a transfer material and a support, are described in Japanese Patent Application Nos. 11-342896 and 11-343665 filed by the present inventors.
The details are described in each specification of the item.

As described above, when the liquid crystal composition containing the photoreactive chiral agent is used, the rate of change of the twisting force of the helical structure of the liquid crystal with respect to the amount of light is large, so that the color width of the selective reflection color that the liquid crystal can exhibit is widened. Blue (B), Green (G), Red with excellent color purity
A color filter consisting of the three primary colors (R) can be obtained.

[Liquid Crystal Display Device] Next, a liquid crystal display device using the color filter of the present invention as described above will be described. The liquid crystal display device of the present invention has at least a color filter, a liquid crystal layer, and a liquid crystal drive electrode between a support substrate and a counter substrate, and as the color filter,
The color filter of the present invention as described above is used. The liquid crystal display device of the present invention is suitably a reflection type liquid crystal display device, but is not limited thereto. For example, a transmission type liquid crystal display device (for example, a transmission type liquid crystal display device as described in JP-A-2000-231097). Device) is also possible.

An example of the liquid crystal display device of the present invention will be described with reference to the drawings, but the present invention is not limited to these. FIG.
1 shows an example of an active matrix type reflection type liquid crystal device. As shown in FIG. 4, when the upper side of FIG.
Wave plate 42, transparent substrate 44, transparent common electrode 46, electrically drivable liquid crystal layer 48, transparent pixel electrode (display electrode)
50, a color filter 52 composed of a cholesteric polarizing element, a light absorbing layer 54, an active element 56 such as a THF (thin film transistor), a metal wiring 58 for electrically connecting the active element, and a support substrate 59 are sequentially arranged. ing. When an MIM is used as an active element, a stripe-shaped transparent electrode is formed as a scanning line on the transparent substrate 44 side. Note that a liquid crystal alignment film, a spacer, a sealant, and the like are usually used in the liquid crystal display device, but these are omitted in FIG.

Although a glass substrate is suitable for the transparent substrate 44 and the support substrate 59, a plastic substrate can be used instead of a glass substrate in order to obtain a liquid crystal display device that is lightweight and hard to break. Transparent electrode (common electrode 4
6, a pixel electrode 50, a scanning line, etc.) is preferably an ITO film.

The polarizing plate 40 and the 波長 wavelength plate 42 are
The polarizing plate 4 is arranged such that the light h1 incident from the observer side is emitted to the transparent substrate 44 side as clockwise or counterclockwise circularly polarized light.
The polarization plane of 0 and the slow axis of the quarter-wave plate 42 are arranged so as to keep an angle of about 45 degrees. In FIG. 4, they are arranged so as to be clockwise circularly polarized light. The quarter-wave plate used here is more preferably a broadband plate that generates a quarter-wave phase modulation over the entire wavelength of visible light.

The liquid crystal layer 48 has an optically isotropic phase when the driving voltage is in the OFF state, and has a retardation of 波長 wavelength in the ON state.

The transparent pixel electrode 50 for applying a voltage to the liquid crystal layer 48 includes an active element (TFT) 56 having a metal wiring 58 through a cholesteric polarizing element 52 and a through hole provided in the light absorbing layer 54. It is connected.

The cholesteric polarizing element 52 is divided into a red reflection area, a green reflection area, and a blue reflection area.
Each region has a helical pitch that selectively reflects the corresponding reflection color.

The light absorbing layer 54 is made of a cholesteric polarizing element 5
A device having a sufficient optical density so as to absorb all the light passing through 2 is disposed between the cholesteric polarizing element 52 and the active element (TFT) 56 and the metal wiring 58. With this arrangement, when no voltage is applied to the liquid crystal layer, circularly polarized light that passes through the color filter (for example, counterclockwise circularly polarized light as described below) is re-reflected by the wiring that connects the active elements. It is possible to prevent circularly polarized light (counterclockwise circularly polarized light) from passing through the color filter and reaching the observer side. Further, it is necessary to maintain electrical insulation between the active elements 56,
It is preferable that the light absorbing layer 54 have insulating properties because the light absorbing layer 54 can serve as both the light absorbing layer and the insulating layer. If the light absorbing layer 54 is not made insulating, it is necessary to provide an insulating layer between the light absorbing layer 54, the active element 56, and the metal wiring 58. The light absorbing layer is preferably a layer that absorbs light having a wavelength in the visible region. For example, carbon black particles can be used as a pigment. Further, an insulating resin is preferably used as the binder polymer of the light absorbing layer, and examples thereof include a polyacetal resin, a polyamide resin, an acrylic resin, and a polycarbonate resin.

Next, the display operation of the reflection type liquid crystal display device having the above configuration will be described with reference to FIG. In FIG. 4, the left side is a state where the driving voltage is OFF, and the right side is a state where the driving voltage is ON with respect to the center broken line.

As shown in FIG. 4, the light beam h1 incident from the observer side is converted into clockwise circularly polarized light by the polarizing plate 40 and the quarter-wave plate. When passing through the transparent substrate 44 and the transparent common electrode 46, this clockwise circularly polarized light enters the liquid crystal layer 48 in a state where no voltage is applied as clockwise circularly polarized light without any modulation. . Liquid crystal layer 48
Is in an optically isotropic state in the state where no voltage is applied, so that light is transmitted without being modulated, and then the light that has passed through the transparent pixel electrode 50 maintains the right circularly polarized state. As it is, it goes to the cholesteric polarizing element (color filter) 52. At this time, assuming that the helical direction and pitch of the cholesteric polarizing element 52 are determined so as to exhibit selective reflection in the red wavelength region, for example, of clockwise circularly polarized light, the incident right circularly polarized light h1 The light h2 of a color other than red passes through the cholesteric polarizing element 52, reaches the light absorbing layer 54, and is absorbed. On the other hand, of the incident right circularly polarized light, the red light cannot pass through the cholesteric polarizing element 52, is reflected as clockwise circularly polarized light h3, and travels toward the observer. The reflected red right circularly polarized light h3 becomes 1 without any modulation for the above-mentioned reason.
When the light reaches the 波長 wavelength plate 42, the 波長 wavelength plate 42 and the polarizing plate 4
By the action of 0, the polarization axis is observed as linearly polarized light parallel to the polarization plane of the polarizing plate 40.

When a voltage is applied to the liquid crystal layer 48, the incident light h4 enters the liquid crystal layer 48 as clockwise circularly polarized light in the same manner as described above. When the voltage is applied, the liquid crystal layer 48 has a half-wave retardation,
The right-handed circularly polarized light is modulated to the left-handed circularly polarized light to form a liquid crystal layer 4.
8, the light passes through all the cholesteric modulation elements 52 that exhibit selective reflection only for clockwise circularly polarized light. Since all the transmitted light is absorbed by the light absorbing layer 54, no light is reflected to the observer as a result.

Next, another embodiment of the present invention will be described with reference to FIG. FIG. 5 shows an example of a reflection type liquid crystal display element of a simple matrix type. As shown in FIG. 5, the reflection type liquid crystal display element has a 波長 wavelength plate 62, a transparent substrate 64, a transparent scanning electrode 66 below a polarizing plate 60, and In this configuration, a drivable liquid crystal layer 68, a transparent signal electrode 70, a color filter 72 composed of a cholesteric polarizing element, a transparent support substrate 74, and a light absorbing layer 76 are sequentially arranged.

The transparent substrate 64, the transparent support substrate 74, the transparent (scanning / signal) electrodes 66 and 70, the polarizing plate 60, 1/4
Wave plate 62, liquid crystal layer 68 and color filter 72
Is the same as that shown in FIG. 1 and functions similarly.

A transparent signal electrode 70 for applying a voltage to the liquid crystal layer 68 is disposed between the color filter 72 composed of a cholesteric polarizing element and the liquid crystal layer 68.

Light absorbing layer 76 Cholesteric polarizing element 72
And a substrate having a sufficient optical density to absorb all the light transmitted through the transparent support substrate 74.
Is disposed on the surface on the side opposite to the cholesteric polarizing element 72.

In the liquid crystal display device shown in FIG. 5, the light beam h1 when no voltage is applied to the liquid crystal layer and the light beam h4 when voltage is applied are reflected or reflected in the same manner as in the liquid crystal display device shown in FIG. Absorbed, h1 is reflected as h3 by the color filter 72 and goes to the observer side,
On the other hand, h4 is entirely transmitted through the color filter, passes through the transparent substrate 74, and is entirely absorbed by the light absorbing layer 76, and the light is not reflected toward the observer.

[0069]

Embodiment 1 In this embodiment, an example of manufacturing a color filter will be described. (1) Preparation of liquid crystal composition A liquid crystal composition having the following composition was prepared.

[0070]

Embedded image

The isotropi of the liquid crystal compound
The point c is 120 ° C. and the nematic point is 85 ° C.

(2) Preparation of Color Filter 1) Preparation of Color Filter Substrate A polyimide alignment film coating solution [LX-140
0 (manufactured by Hitachi Chemical DuPont) in a 1: 1: 1 mixed solvent of N-methyl-2-pyrrolidone: 2-butoxyethanol: diethylene glycol monoethyl ether] using a spin coater. , 1000
The solution was applied at rpm, dried in an oven at 100 ° C. for 30 minutes, and cured in an oven at 250 ° C. for 30 minutes to form an alignment film. Further, the surface of the film was subjected to an orientation treatment by a rubbing treatment to produce a glass substrate with an orientation film.

2) Formation of Color Filter Layer On the alignment film of the glass substrate provided with the alignment film prepared in 1) above,
The liquid crystal composition of the above (1) was prepared using a spin coater for 600 minutes.
At about rpm, the applied layer is applied to be about 2 μm,
This was dried in an oven at 100 ° C. for 30 minutes to form a liquid crystal layer. Next, the liquid crystal layer was heated to 85 by a hot plate.
° C (point N), and then the substrate provided with the liquid crystal layer is brought into contact with a metal plate kept at room temperature, thereby rapidly cooling to room temperature (cooling from 85 ° C to 25 ° C in about 1 minute).
did. A transparent solid liquid crystal layer was formed. On the transparent layer, the transmittance is different in three stages (0%, 46%, 92%).
%), A photomask in which each region is arranged corresponding to a red pixel, a green pixel, and a blue pixel and a 350 nm
An ultra-high pressure mercury lamp was arranged via a band pass filter having a center at the center, and irradiation was performed with the ultra high pressure mercury lamp through this photomask and the band pass filter to perform patterning.
The irradiation energy at this time is mJ /
cm ² , and the irradiation intensity was 4.2 mW / cm ² .
The irradiation time was 20 seconds. In this state, selective reflection was already observed. Thereafter, the photomask and the bandpass filter were removed, and the liquid crystal layer was heated by a hot plate and kept at the iso point of 120 ° C. for 30 seconds. Thereafter, the liquid crystal layer was cooled to 85 ° C., which is the N point, by a hot plate kept at 85 ° C., and kept at that temperature for 30 seconds.

Next, with the liquid crystal layer kept at 85 ° C.,
The entire surface was exposed for 20 seconds at an irradiation intensity of 11.4 mW / cm ² by an ultra-high pressure mercury lamp through a band-pass filter having a center at 0 nm to polymerize and cure the liquid crystal layer. Further, in order to accelerate the curing of the color filter layer, the color filter layer was baked in an oven at 220 ° C. for 20 minutes to obtain a color filter having high color purity, in which red, green, and blue pixel patterns were formed.

Example 2 In the method of manufacturing a color filter of Example 1, after exposure for causing a photoreaction, photopolymerization was carried out at room temperature (25 ° C.) without heating, without heating. Further, in order to accelerate the curing of the color filter layer, the color filter layer was baked in an oven at 220 ° C. for 20 minutes to obtain a color filter having high color purity, in which red, green, and blue pixel patterns were formed.

Comparative Example 1 In the method of manufacturing the color filter of Example 1,
A color filter was prepared in the same manner as in Example 1 except that a liquid crystal layer was formed by coating and drying, and then the film was exposed as it was without performing a transparentizing process. As a result, selective reflection occurred in a region extending outside the opening of the exposure mask, resulting in low resolution.

Example 3 A liquid crystal display device having a structure as shown in FIG. 5 was manufactured using the same color filters as those in Example 1. (1) Preparation of transparent support substrate A borosilicate glass substrate having a thickness of 1.1 mm was washed and dried. (2) Formation of light absorbing layer, color filter layer, transparent signal electrode and alignment film on transparent support substrate Light absorption including carbon black and insulating resin (polyvinyl butyral) on transparent support substrate prepared in (1) above A layer solution (30% by mass of carbon black was added to the insulating resin) was applied by spin coating and dried so as to have a dry thickness of 2 μm. A color filter was formed on the surface of the transparent support substrate opposite to the light absorbing layer in the same manner as in Example 1. Next, an ITO film having a thickness of 0.1 μm was formed on the color filter layer by a sputtering method, and then a pattern was formed by a conventional photolithography method, thereby forming a stripe-shaped transparent signal electrode. A coating solution of a polyimide alignment film (LX-1400, manufactured by Hitachi Chemical DuPont) is applied to the transparent signal electrode by a spin coater, dried in an oven at 100 ° C. for 5 minutes, and then dried.
Baking in an oven at ℃ for 1 hour to form an alignment film.
The surface of the film was subjected to an alignment treatment by a rubbing treatment. (3) Preparation of Transparent Substrate (Counter Substrate) An ITO film was formed on a counter glass substrate having a thickness of 1.1 mm by a sputtering method to a thickness of 0.1 μm by a sputtering method. A transparent scanning electrode was formed, and an alignment process was performed in the same manner as the above-described alignment process. (4) Production of Liquid Crystal Cell After the alignment treatment surface side of the transparent support substrate provided with the color filter and the like and the orientation treatment surface side of the counter substrate were separated by a space of 2 μm, liquid crystal was injected. The liquid crystal used had a homeotropic alignment when the voltage was ON, and the retardation was halved when the voltage was OFF. A quarter-wave plate (Sumikalite, manufactured by Sumitomo Chemical Co., Ltd.) and a polarizing plate (SH-1832AW, manufactured by Sumitomo Chemical Co., Ltd.) were adhered to the counter substrate side of the liquid crystal cell via an adhesive. Since the liquid crystal display device thus manufactured uses a color filter with high resolution, excellent color display was possible.

[0078]

In the method for producing a color filter of the present invention, the liquid crystal layer is subjected to a transparency treatment prior to the step of imagewise irradiating light in the photosensitive wavelength region of the photoreactive chiral agent. A color filter with high resolution can be obtained. The liquid crystal display device incorporating such a color filter can perform excellent color display.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a part of a process of manufacturing a liquid crystal color filter of the present invention.

FIG. 2 is a schematic view showing a part of a process of manufacturing a liquid crystal color filter of the present invention.

FIG. 3 is a schematic view showing a part of a process of manufacturing a liquid crystal color filter of the present invention.

FIG. 4 is a conceptual diagram showing an example of an active matrix type liquid crystal display device of the present invention. The left side of the dashed line indicates the reflection or absorption of circularly polarized light in the voltage OFF state, and the right side thereof indicates the voltage ON state.

FIG. 5 is a conceptual diagram showing an example of a simple matrix type liquid crystal display device of the present invention.
The right side of the state shows the reflection or absorption of the circularly polarized light in the voltage ON state, respectively.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Temporary support 12 Cushion layer 14, 24 Orientation film 16 Liquid crystal layer 18 Cover film 20 Transfer material 22 Substrate 26 Color filter substrate 28 Exposure mask 40, 60 Polarizing plate 42, 62 1/2 wave plate 44, 64 Transparent substrate 46 Transparent common electrode 48, 68 Liquid crystal layer 50 Transparent pixel electrode 52, 72 Color filter 54, 76 Light absorption layer 56 TFT element 58 Metal wiring 59, 74 Support substrate 66 Transparent scanning electrode 70 Transparent signal electrode

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H048 BA43 BA47 BA64 BB02 BB42 2H049 BA02 BA03 BA05 BA07 BA43 BB03 BC22 2H091 FA01Y FB02 LA15 LA17 LA30

Claims (7)

[Claims] 1. A step of forming a liquid crystal layer containing at least a liquid crystalline compound having at least one polymerizable group and a photoreactive chiral agent, wherein light in the photosensitive wavelength region of the photoreactive chiral agent of the liquid crystal layer is formed. A method for producing a color filter, comprising at least a step of irradiating imagewise and a step of photopolymerizing a liquid crystalline compound having at least one polymerizable group, wherein the photoreactive chiral agent is in a photosensitive wavelength region. A method for producing a color filter, wherein a transparentizing treatment is performed on the liquid crystal layer prior to the step of irradiating light imagewise. 2. The method for producing a color filter according to claim 1, wherein the transparentizing treatment includes a step of heating the liquid crystal layer and a subsequent quenching step. 3. The method for producing a color filter according to claim 1, wherein the heating is performed so that the temperature is in a temperature range in which the liquid crystal compound exhibits a nematic phase state. 4. The method for producing a color filter according to claim 1, wherein the step of photopolymerizing is performed at room temperature. 5. The method for producing a color filter according to claim 1, wherein the liquid crystal layer further contains a photopolymerization initiator. 6. A color filter produced by the method for producing a color filter according to any one of claims 1 to 5. 7. A liquid crystal display device comprising at least one of a color filter, a liquid crystal layer, and a liquid crystal drive electrode between a pair of substrates that are light-transmissive, wherein the color filter is the color filter according to claim 6. A liquid crystal display device, characterized in that: