JP4380762B2 - Liquid crystal display device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a color filter substrate used in a liquid crystal display device and other display devices, and a manufacturing method thereof. In particular, the present invention relates to a matrix-type color liquid crystal display device used by being incorporated in a flat image display device or the like.

  In recent years, liquid crystal display devices have been highly evaluated for their space-saving properties, light weight, and power-saving properties due to their thinness, and recently, they are rapidly spreading to portable devices and television applications. A liquid crystal display device can perform multicolor display by providing a color filter substrate in the panel structure, and generally performs RGB three-color display or six-color display in which RBG pixels for reflection are added thereto. Is.

  By the way, as a liquid crystal display device for portable devices, a reflective type or a transflective type liquid crystal display device in which a reflective part is partially formed may be adopted in order to ensure visibility even under strong outdoor light in the daytime. Many. In such a case, in order to effectively utilize the reflected light, a λ / 4 retardation film, a λ / 2 retardation film, or the like is incorporated in the liquid crystal panel configuration as a member that forms part of the absorption-type circularly polarizing plate. .

  However, since such a retardation film usually has the same retardation value in the plane, when the liquid crystal display device in which the retardation film is incorporated is colored by a color filter substrate, the light passing through the display area of each color pixel is transmitted. Due to the difference in wavelength range, a problem that appropriate phase difference control becomes difficult occurs.

  For example, in a reflective or transflective liquid crystal display device for portable devices, a retardation film having an in-plane retardation (approximately 138 nm) of λ / 4 in a green wavelength region (center wavelength around 550 nm) is combined with a linear polarizing plate. When used as a circularly polarizing plate, the blue wavelength range (center wavelength around 450 nm) is more than λ / 4, and the red wavelength range (center wavelength around 630 nm) is insufficient relative to λ / 4. In a pixel, complete circular polarization cannot be obtained.

  Further, in the transflective liquid crystal display device, as described above, the retardation film having an in-plane retardation of λ / 4 is used for the reflection part display, but this often impairs the display quality of the transmission part. There is also a problem of end. This problem is that the λ / 4 in-plane retardation is not required in the transmission part in the first place, but the λ / 4 retardation film is interposed between the viewing side substrate and the polarizing plate in order to correspond to the reflection part display. This is due to the fact that a λ / 4 retardation film is also disposed between the substrate on the backlight side and the polarizing plate for compensation of display of the transmissive portion, regardless of the reflective portion. That is, in the transmission part, if the retardation of the two λ / 4 retardation films is exactly the same, there is no influence on the display quality in principle. This causes a shift in the contrast and lowers the contrast.

  To solve this problem, (1) a method for solving the problem by optical compensation using a retardation plate outside the liquid crystal cell, and (2) a problem that optical compensation is performed by providing a retardation layer inside the liquid crystal cell. A method for solving this problem is known.

  Patent document 4 is mentioned as an example of the former (1). In Patent Document 4, a phase difference plate is provided separately from a color filter substrate, and “this phase difference plate distributes three different phase difference regions corresponding to three basic color pixels forming a color display”. However, according to this method, since a distance is generated between the color filter substrate and the retardation substrate, it is difficult to accurately perform optical compensation particularly in display in an oblique direction.

  As an example of the latter (2), a phase difference element having a phase difference amount corresponding to a display pixel of three colors by forming a film of a polymerization type liquid crystal material having a different film thickness or different types has been devised. (For example, refer to Patent Document 1).

  In addition, the thickness of the light transmissive pattern of the color filter is formed to be different for each color, and a retardation control layer (such as a liquid crystalline polymer) is formed thereon, and the total thickness of the color filter layer and the retardation control layer is A color filter having a phase difference control layer having a phase difference amount corresponding to display pixels of three colors by being laminated so as to be constant has been devised (see, for example, Patent Document 2).

  Furthermore, the thickness of the light transmissive pattern of the color filter is formed to be different for each color and further in the transmissive part / reflective part. By laminating the retardation layer so that it is flattened and the orientation direction is different, there is no phase difference in the transmission part and there is a phase difference in the reflection part and a value corresponding to each color (respectively A liquid crystal display device having λ / 4) has also been devised (for example, see Patent Document 3).

However, these conventional methods must be said to be inappropriate as a method for easily and sufficiently solving the problem of the phase difference.
For example, in Patent Document 1, as a means for changing the thickness of the retardation layer for each region, a polymerization-type liquid crystal material is formed, and this is exposed to radiation such as ultraviolet rays by changing the irradiation amount for each region. However, in this method, the final film thickness greatly depends on the development conditions, particularly when uncured components remain in the thin film. It is very difficult to obtain a desired film thickness stably by controlling. In addition, when patterning different types of polymerizable liquid crystal materials using a photolithography method, a printing method, or the like, a process is required for each type, and thus it cannot be easily manufactured.

  In Patent Document 2, since the thickness of the retardation layer is determined by the thickness of the color filter layer serving as a base, the difficulty in the film formation process of the retardation layer is somewhat eliminated. There is a problem that the film thickness needs to be strictly controlled, and the design of the color filter is restricted or the difficulty of the manufacturing process of the color filter is increased. In the first place, it is not so easy to form a retardation layer on a color filter layer having a thickness difference so as to keep the total thickness of the retardation layer and the color filter layer uniform.

The problem in forming a retardation layer so as to flatten the color filter by providing a step in the color filter in Patent Document 3 is the same as that in Patent Document 2. As a means for differentiating the alignment method of the retardation layer, a method of forming an alignment film in which the alignment direction is made different between the reflection part and the transmission part by photo-alignment treatment, or the alignment direction is made different between the reflection part and the transmission part by mask rubbing. Although a method for forming an oriented alignment film is shown, it is necessary to perform polarized light exposure or non-polarized parallel light oblique exposure to perform photo-alignment processing. In order to carry out, the process involving physical contact must be carried out a plurality of times, and a decrease in yield is inevitable.
JP 2004-191832 A JP 2005-24919 A JP 2006-85130 A Japanese Patent No. 3687862

  The present invention has been made to solve the above problems, and provides a liquid crystal display device having an optical compensation capability capable of solving the phase difference problem that occurs when multicolor display is performed by a color filter. It is another object of the present invention to provide a method for manufacturing the liquid crystal display device easily and with high quality.

A configuration of the present invention for solving the above-described problems is shown below.
(Claim 1)
At least a first substrate, a second substrate facing the first substrate, and a first polarizing plate disposed on a surface opposite to the second substrate of both surfaces of the first substrate; A second polarizing plate disposed on a surface opposite to the first substrate of both surfaces of the second substrate so that an absorption axis direction is 90 ° different from that of the first polarizing plate; A liquid crystal layer sandwiched between one substrate and the second substrate, and a color filter layer provided between the first substrate and the liquid crystal layer, wherein the color filter layer comprises: The pixel includes a plurality of pixels of two or more colors, each of which includes a reflection part and a transmission part, and a retardation thin film made of a liquid crystal fixing layer is provided between the first substrate and the second substrate. The color filter layer is composed of a large number of pixels of two or more colors, and each pixel is opposite to each other. A retardation film comprising a liquid crystal immobilization layer between the first substrate and the second substrate, wherein the retardation film comprises at least one layer of the pixels, The birefringence differs depending on the color and / or the region corresponding to the reflection part / transmission part due to the difference in the degree of orientation of the liquid crystal fixing layer. The liquid crystal display device has an in-plane birefringence satisfying the formula (1) and the formula (2) in a region corresponding to the transmission portion of the pixel.
(1) 0.75 ≦ Δn [fr] / λd [fr] ≦ 1.35
(Where λd [fr] = (d [f1] × λ [f2]) / (d [f2] × λ [f1]))
(2) Δn [t] <1.2 × 10 ⁻³
(Where Δn [t] is the in-plane birefringence in the region corresponding to the pixel transmitting portion, and Δn [fr] is the in-plane birefringence in the region corresponding to the pixel reflecting portion of a certain color (hereinafter referred to as color 1). Is the ratio of the in-plane birefringence in the region corresponding to the pixel reflection portion of any other color (hereinafter color 2), and d [f1] and d [f2] are the pixel reflections of color 1 and color 2, respectively. The thickness of the retardation layer in the region corresponding to the part, λ [f1] · λ [f2] is the center wavelength of the color of the pixel reflection part of color 1 and color 2, respectively.
(Claim 2)
The liquid crystal display device according to claim 1, wherein the retardation film having the in-plane birefringence has substantially the same slow axis direction in any region.
(Claim 3)
3. The liquid crystal display device according to claim 1, wherein the liquid crystal sandwiched between the two substrates is aligned substantially perpendicular to the two substrates when no voltage is applied.
(Claim 4)
The liquid crystal display device according to claim 1, wherein the retardation film is formed by polymerizing and / or crosslinking a compound containing a thermotropic liquid crystal.
(Claim 5)
In the manufacturing method of the liquid crystal display device according to claim 1, at least
(A) A state in which a solution containing a compound exhibiting thermotropic liquid crystallinity and capable of being polymerized and / or cross-linked by light is applied onto the first substrate, and the liquid crystal compound is aligned in a predetermined direction. Forming a thin film of
(B) irradiating the first substrate with light so as to have a different irradiation amount for each region corresponding to a predetermined pattern of each color of the color filter;
(C) heating the first substrate to a temperature equal to or higher than the isotropic phase transition temperature of the liquid crystal compound;
(D) exposing the entire surface of the first substrate while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase;
(E) making the first substrate and the second substrate face each other and enclosing a liquid crystal compound;
The manufacturing method of the liquid crystal display device with a phase difference thin film characterized by including these.
(Claim 6)
(A) A solution containing a compound that exhibits thermotropic liquid crystallinity and that can be polymerized and / or cross-linked by light is applied onto the first substrate, and the liquid crystal compound is aligned in a predetermined direction. 6. The method of manufacturing a liquid crystal display device according to claim 5, wherein the step of forming a thin film in a state is performed so that the thickness of the thin film is uniform over the entire substrate.
(Claim 7)
(A) A solution containing a compound that exhibits thermotropic liquid crystallinity and that can be polymerized and / or cross-linked by light is applied onto the first substrate, and the liquid crystal compound is aligned in a predetermined direction. Forming a thin film in a state,
On the first substrate, a solution containing a compound having thermotropic liquid crystallinity and capable of being polymerized and / or cross-linked by either light or heat was applied, and the liquid crystal compound was aligned in a predetermined direction. Forming a thin film in a state, and
(D) a step of exposing the entire surface of the first substrate while maintaining the temperature at which the liquid crystal compound is maintained in an isotropic phase;
7. The step of heating the first substrate to a temperature that is equal to or higher than an isotropic phase transition temperature of the liquid crystal compound and higher than polymerization and / or crosslinking is performed. A method for producing a liquid crystal display device according to claim 1.
(Claim 8)
(D) a step of exposing the entire surface of the first substrate while maintaining the temperature at which the liquid crystal compound is maintained in an isotropic phase;
While the first substrate is maintained at a temperature higher than that at which the liquid crystal compound is kept in an isotropic phase, light irradiation is performed on portions other than the region irradiated with light at the maximum irradiation amount in the step (b). The method of manufacturing a liquid crystal display device according to claim 5, wherein:
(Claim 9)
9. The amount of irradiation when performing light irradiation while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase in claim 8, including the light irradiation in the step (b) in each region. The method for manufacturing a liquid crystal display device is characterized in that the exposure amount is the same as the exposure amount of the region irradiated with light at the maximum irradiation amount in the step (b).
(Claim 10)
The method for manufacturing a liquid crystal display device according to claim 5, wherein a color filter layer is formed on the first substrate before the step (a) is performed.
(Claim 11)
The method for manufacturing a liquid crystal display device according to claim 5, wherein a color filter layer is formed on the first substrate after performing the step (d).
(Claim 12)
The steps (a) to (d) applied to the first substrate are all applied to the second substrate, and a TFT layer is formed on the second substrate before performing the step (a). The method for manufacturing a liquid crystal display device according to claim 5, further comprising a step of:

According to the first aspect of the present invention, in the liquid crystal display device, a liquid crystal fixing layer is provided between the first substrate and the second substrate, so that a retardation film or the like is separately provided outside the two substrates. Unlike the conventional configuration provided in the above, it is possible to provide a phase difference suitable for each region of the color of the pixel and the reflection part / transmission part without being affected by the parallax problem. By providing each according to the difference, the above-mentioned phase difference problem can be solved even with a single-layer thin film formed integrally on the entire surface of the substrate.
Further, according to the invention described in claim 1, in the above, the problem caused by the phase difference can be solved by controlling the birefringence value to a stricter and optimum value. It was.
According to the second aspect of the present invention, the liquid crystal immobilization layer is provided so that the birefringence differs depending on the degree of orientation for each color even if the slow axis is in the same direction. Therefore, by aligning the liquid crystal compound by a simple method such as rubbing the alignment film in a certain direction, it becomes possible to perform optimum phase difference compensation for each color, and solve the above phase difference problem I was able to.
According to the third aspect of the present invention, it is possible to provide a VA or MVA drive type liquid crystal display device that provides a black display in which leakage light is suppressed, particularly when no voltage is applied.
According to the invention described in claim 4, since the thermotropic liquid crystal is used for the liquid crystal fixing layer, the liquid crystal display using the color filter substrate in which the above-mentioned anisotropy differs for each color by using heat treatment. The device could be manufactured.
According to the fifth aspect of the present invention, it is possible to reliably form liquid crystal compound layers having different phase differences for each color, and to obtain a liquid crystal display device having excellent display characteristics.
According to the sixth aspect of the invention, the process can be facilitated by making the film thickness uniform.
According to the seventh aspect of the present invention, the liquid crystal immobilization layer having different refractive index anisotropy for each color region can be formed more accurately and easily.
According to the eighth aspect of the invention, an undesirable reaction caused by overexposure can be suppressed by avoiding the occurrence of a region where the light irradiation amount is excessive.
According to the ninth aspect of the invention, by making the total light irradiation amount by each color region uniform, an undesirable reaction caused by overexposure can be more reliably suppressed.
According to the tenth aspect of the invention, since the liquid crystal fixing layer is formed after the color filter layer is formed on the substrate, the phase difference caused by the color filter layer can be more reliably eliminated.
According to the eleventh aspect of the invention, since the color filter layer is formed after the liquid crystal fixing layer is formed on the substrate, the alignment control of the liquid crystal compound can be reliably performed on the substrate.
According to the twelfth aspect of the invention, since the liquid crystal fixing layer is formed on the TFT layer, the alignment control of the liquid crystal compound can be performed in a situation where there are few steps in the lower layer compared to the case of forming on the color filter layer. The liquid crystal immobilization layer could be formed while suppressing the influence of heat in the subsequent process as compared with the case where it was formed under the color filter layer.

The display panel constituting the liquid crystal display device has a structure in which a liquid crystal material is sealed between two transparent substrates. In the present invention, either one is the first substrate, and the substrate facing this is the second substrate. Of the two opposite surfaces (opposing surfaces) of these transparent substrates, a black matrix, a color filter, a counter electrode, an alignment film, etc. are usually formed on one surface side, and a TFT is formed on the other surface side. (Thin film transistor), a pixel electrode, an alignment film, and the like can be formed. Further, a polarizing plate is attached to a surface opposite to the facing surface of each transparent substrate. These two polarizing plates are usually arranged so that the polarizing axes of the polarizing plates are perpendicular to each other (the angle between the respective absorption direction axes is 90 degrees). It is possible to obtain a liquid crystal display device that satisfies the gist of the present invention even by a configuration in which polarizing plates are arranged in parallel to each other, but this configuration is not often employed because black display leakage light increases and display quality deteriorates. Not.
As a method for sealing liquid crystal between two substrates, a dip injection method and a drop injection method are known. In the present invention, a known configuration described in, for example, Japanese Patent No. 3874895 can be used as the configuration of the TFT, pixel electrode, counter electrode, alignment film, polarizing plate, and the like.

A substrate on which a thin film formed by polymerizing and / or cross-linking a liquid crystal fixing layer, that is, a solution containing a compound having liquid crystallinity, is formed on a flat body, which constitutes a part of the liquid crystal display device of the present invention. As for such a substrate, not only the color filter substrate and the TFT substrate but also the liquid crystal fixing layer itself can be used as a self-holding type retardation substrate and retardation film. Examples of the material used for the planar body include glass, plastic, and film base material.
Hereinafter, as an example, a color filter substrate in which the liquid crystal compound is stacked on a color filter layer on which display pixels are formed to form a liquid crystal fixing layer will be described.

FIG. 19 shows an example (part) of a color filter substrate constituting a part of the liquid crystal display device of the present invention. This color filter substrate has a structure in which a color filter layer and a liquid crystal fixing layer (retardation thin film) are laminated on a glass substrate, and the retardation thin film has a plurality of regions in the plane. The liquid crystal compound layers are polymerized and / or crosslinked and fixed in different states. For example, the region R (4a) is almost completely oriented and the birefringence is most strongly expressed, and the region G (4b) is in a state of lower orientation than the region R and the birefringence is relatively low. The region B (4c) is weak and has a lower degree of orientation than the region G, and has the least birefringence. As described above, the degree of orientation can be estimated from the change in birefringence.

When the degree of orientation of the liquid crystal fixing layer is different, the birefringence of the region is also different, and the amount of retardation is also a different value.
Although the color filter substrate and the liquid crystal immobilization layer are sequentially laminated here for the configuration of the color filter substrate, the liquid crystal immobilization layer may be provided under the color filter layer, or the configuration of only the color filter layer. It is good. When a liquid crystal immobilization layer is provided under the color filter layer, the order of glass substrate / liquid crystal immobilization layer / black separation wall / colored composition layer is also the order of glass substrate / black separation wall / liquid crystal immobilization layer / coloration. The order of the composition layers may be used, and when only the color filter layer is used, a retardation film can be provided on the opposite substrate (usually a TFT substrate). Furthermore, it is of course possible to provide a structure in which a retardation film is provided on the color filter substrate and a retardation film is provided on the opposite substrate.

In the present invention, the “degree of orientation” describes what is in each of the in-plane regions, and does not necessarily mean that the degree of orientation is constant in the thickness direction. For example, in a certain region, the vicinity of the lower surface may be in a more aligned state, and the vicinity of the upper surface may be in a more non-oriented state. In this case, the “degree of orientation” roughly indicates the average degree of orientation in the thickness direction.

The type of retardation to be expressed, that is, the type of liquid crystal alignment in the present invention, is not particularly limited. For example, a positive A plate obtained by homogeneous alignment in which rod-shaped liquid crystals are aligned so as to be horizontal in the plane, a positive C plate obtained by homeotropic alignment aligned so as to be perpendicular to the plane, and horizontal in the plane. In addition, a negative C plate obtained by cholesteric alignment with a spiral wound, a negative A plate obtained by homeotropic alignment aligned so as to be perpendicular to the plane in the case of a disc-like liquid crystal, and horizontal in the plane However, the present invention is not limited to this, and the present invention is not limited to these. Biaxiality in which the rod-like liquid crystal is horizontal in the plane and spirals and the azimuth is deflected (positive A plate / The present invention is applicable to any orientation that may exist, such as those of negative C-plate composites).

In the color filter substrate related to the present invention, one of the regions may be optically substantially isotropic by fixing the liquid crystal in a non-oriented state. Since the liquid crystal fixing layer region is substantially free of retardation, it functions as a simple transparent thin film.

In the present invention, the retardation film may be composed of a plurality of layers. At least one layer of the retardation film has an in-plane birefringence satisfying Equation (1) in the region corresponding to the reflective portion of the pixel and Equation (2) in the region corresponding to the transmissive portion of the pixel. In such a case, in the transflective liquid crystal display device using a color filter including a reflective portion and a transmissive portion in the pixel, the problem of the phase difference can be compensated more appropriately.
(1) 0.75 ≦ Δn [fr] / λd [fr] ≦ 1.35
(Where λd [fr] = (d [f1] × λ [f2]) / (d [f2] × λ [f1]))
(2) Δn [t] <1.2 × 10 ⁻³
(Where Δn [t] is the in-plane birefringence in the region corresponding to the pixel transmitting portion, and Δn [fr] is the in-plane birefringence in the region corresponding to the pixel reflecting portion of a certain color (hereinafter referred to as color 1). Is the ratio of the in-plane birefringence in the region corresponding to the pixel reflection portion of any other color (hereinafter color 2), and d [f1] and d [f2] are the pixel reflections of color 1 and color 2, respectively. The thickness of the retardation layer in the region corresponding to the part, λ [f1] · λ [f2] is the center wavelength of the color of the pixel reflection part of color 1 and color 2, respectively.

The retardation film of the present invention is intended to control the phase difference to a desired value by making the birefringence of the liquid crystal fixing layer different for each region. Even if it exists, it is not necessary to change the film thickness of the said layer. Therefore, it is possible to make the plurality of regions have substantially the same film thickness, that is, the same film thickness in the entire retardation film. Of course, the thickness may be different for each region.

Various means for obtaining a color filter substrate related to the present invention are conceivable, but an existing color filter manufacturing method can be used as a method for forming a color filter layer.
As an example, a case will be described in which a colored composition in which a pigment is dispersed in a pigment carrier is formed in a predetermined region for each color and cured to form a pixel.

As the pigment contained in the colored composition, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for a coloring composition is shown with a color index number.
Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, Red pigments such as 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 can be used, and a yellow pigment can also be used in combination. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 , 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 198, 213, 214 and the like.

Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37 or the like can be used, and a yellow pigment can be used in combination. As the yellow pigment, the same pigments as those mentioned for the red coloring composition can be used.

Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like can be used, and a purple pigment can be used in combination. Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like.

It is also possible to use an inorganic pigment as the pigment, specifically, metals such as yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, etc. Examples thereof include oxide powder, metal sulfide powder, and metal powder. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The coloring composition can contain a dye within a range that does not reduce heat resistance for color matching.

The pigment carrier contained in the colored composition is for dispersing a pigment, and is composed of a transparent resin such as a thermoplastic resin, a thermosetting resin, or a photosensitive resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Alternatively, two or more kinds can be mixed and used.
The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition. When a mixture of a transparent resin and its precursor is used as a pigment carrier, the transparent resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the pigment in the coloring composition. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

Monomers and oligomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, various acrylic esters such as epoxy (meth) acrylate and methacrylic acid Examples thereof include esters, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

When the composition is cured by irradiation with ultraviolet rays or the like, a photopolymerization initiator or the like is added to the coloring composition.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- Acetophenone photopolymerization initiators such as 1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 − Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone photopolymerization initiators such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis (trichloro Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.
A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigments in a coloring composition, Preferably it is 10-150 weight part.

The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
The sensitizer can be contained in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

Furthermore, the coloring composition can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimerca DOO -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.
The polyfunctional thiol can be used in an amount of 0.2 to 150 parts by weight, preferably 0.2 to 100 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

Furthermore, in the coloring composition, the pigment is sufficiently dispersed in the pigment carrier, and applied to a flat body such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form each color display pixel. A solvent can be included for ease. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.
The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

The coloring composition comprises one or more pigments, if necessary, together with the above photopolymerization initiator, in a pigment carrier and an organic solvent, such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. It can be produced by finely dispersing using a dispersing means. Moreover, the coloring composition containing 2 or more types of pigments can also be manufactured by mixing each pigment separately finely dispersed in a pigment carrier and an organic solvent. When the pigment is dispersed in the pigment carrier and the organic solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition comprising a pigment dispersed in a pigment carrier and an organic solvent using a dispersion aid is used. If so, a color filter excellent in transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

The dye derivative is a compound in which a substituent is introduced into an organic dye, and is preferably close to the hue of the pigment to be used. However, if the addition amount is small, those having different hues may be used. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. You can use what you have. In particular, a pigment derivative having a basic group is preferably used because it has a large pigment dispersion effect. These can be used alone or in admixture of two or more.

The coloring composition can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.
The storage stabilizer can be contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

In addition, the coloring composition may contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the substrate.
Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.
The silane coupling agent can be contained in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

The coloring composition can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, ink jet printing ink, solvent development type or alkali development type colored resist. The colored resist is obtained by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and an organic solvent.
The pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the colored composition (100% by weight). More preferably, it is contained in a proportion of 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by a pigment carrier.
The colored composition is removed by means of centrifugal separation, sintering filter, membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to carry out.

The color filter related to the present invention includes display pixels of a plurality of colors formed on a plane body by a printing method or a photolithography method.
As the planar body, a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the planar body for driving the liquid crystal after forming the liquid crystal panel. Furthermore, a liquid crystal immobilization layer may be formed on the plane body first.

The formation of each color display pixel by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above-mentioned various printing inks, so the color filter manufacturing method is low cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

When forming each color display pixel by the photolithography method, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a flat body by spray coating, spin coating, slit coating, roll coating or the like. By a method, it apply | coats so that a dry film thickness may be set to 0.2-10 micrometers. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.
If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter layer in the color filter related to the present invention can be produced by an ink jet method, an electrodeposition method, a transfer method or the like in addition to the above method. The ink jet method is a method of forming display pixels by ejecting and landing each color ink with a fine nozzle in a region partitioned by a light-shielding separation wall formed on a flat body. The electrodeposition method is a method in which each color display pixel is electrodeposited on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a planar body. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired flat body.

Next, a method for obtaining the liquid crystal immobilization layer of the present invention will be described. Various means can be considered as in the case of forming the color filter layer, but a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or crosslinked by light is applied on the substrate, It is simple to cure by using both exposure and heating.

In addition to the above liquid crystal compound and solvent, the solution is chiral agent, photopolymerization initiator, thermal polymerization initiator, sensitizer, chain transfer agent, polyfunctional monomer or oligomer, resin, surfactant, storage stabilizer, adhesion improvement Agents and other necessary materials can be added as long as the liquid crystal compound does not lose liquid crystallinity.
Examples of the thermotropic liquid crystal include, for example, alkylcyanobiphenyl, alkoxybiphenyl, alkylterphenyl, phenylcyclohexane, biphenylcyclohexane, phenylbicyclohexane, pyrimidine, cyclohexanecarboxylic acid ester, halogenated cyanophenol ester, alkylbenzoic acid ester, alkyl Cyanotolane, dialkoxytolane, alkylalkoxytolane, alkylcyclohexyltolane, alkylbicyclohexane, cyclohexylphenylethylene, alkylcyclohexylcyclohexene, alkylbenzaldehyde azine, alkenylbenzaldehyde azine, phenylnaphthalene, phenyltetrahydronaphthalene, phenyldecahydronaphthalene, triphenylene, pentaeth Rubenzen and derivatives thereof, and can be exemplified acrylate of the compound.
Photopolymerization initiators, sensitizers, chain transfer agents, polyfunctional monomers or oligomers, resins, surfactants, storage stabilizers, adhesion improvers, and the like are the same as the compounds used in the above-described coloring composition. be able to.
As the solvent, the same solvent as that used in the above-described coloring composition can be used.

Next, this solution is applied on a flat body. At this time, if necessary, a film having orientation ability is formed on the surface of the planar body, or treatment is performed so that the surface of the planar body itself exhibits an orientation regulating force. For coating, spin coating method, slit coating method, letterpress printing method, screen printing, lithographic printing, reversal printing, gravure printing and other printing methods or methods combining these printing methods with an offset method, ink jet method, bar coating Other known film forming methods can be applied.

The type of the planar body is not particularly limited, but when the liquid crystal display device of the present invention is used by incorporating a substrate on which a liquid crystal immobilization layer is formed, the planar body is a glass plate or a resin plate, or those A light transmissive substrate such as a color filter substrate on which display pixels are formed or a TFT substrate on which drive elements are formed is suitable. In addition, a light-transmitting film such as a plastic film can be used as the planar body.

Subsequently, after the formed solution is dried to form a liquid crystal compound layer, pattern exposure is performed with a different dose for each region. As a result, the region irradiated with a sufficient amount of light to polymerize and / or crosslink the liquid crystal is fixed while maintaining its alignment state, and the region irradiated with a smaller amount of light is fixed. A part of the uncured component remains fixed and is not irradiated with light, and the entire region remains unreacted. For the exposure, radiation such as ultraviolet rays, electron beams, visible rays, and infrared rays can be used. In the present invention, “light” refers to one or a plurality of types of the radiation, and expressions such as “polymerization by light” and “photopolymerization” also mean characteristics relating to one or a plurality of types of the radiation. Is.

In this way, the substrate exposed with a different dose depending on the region is heated to a temperature equal to or higher than the isotropic phase transition temperature of the liquid crystal compound. Then, the region of the liquid crystal compound layer that has not been irradiated with light transitions to an isotropic phase and becomes substantially non-oriented, and the region that has been irradiated with an insufficient amount of light remains in accordance with the amount of irradiation. The orientation of the curing component is disturbed, resulting in a low orientation state. A region irradiated with a sufficient amount of light is in a state of being fixed while maintaining its orientation, that is, in a highly oriented state.

Finally, when the entire surface of the substrate is exposed while maintaining the temperature at which the liquid crystal compound is maintained in the isotropic phase, the non-aligned region, the low-aligned region, and the highly-aligned region are polymerized as they are. And / or cross-linked and immobilized. Thereby, a retardation film having a different degree of orientation for each region can be obtained. For some liquid crystal compounds, the lower limit of the temperature at which the isotropic phase is maintained is lower than the isotropic phase transition temperature. Therefore, when using such a liquid crystal compound, the temperature during the entire surface exposure is first heated. However, it is usually convenient to heat the thin film above the isotropic phase transition temperature and expose the entire surface while maintaining the temperature. In this overall exposure, a sufficient amount of light is irradiated to polymerize and / or crosslink the liquid crystal compound.

As another means for obtaining a substrate on which a liquid crystal immobilization layer related to the present invention is formed, the liquid crystal used in the liquid crystal solution exhibits a thermotropic liquid crystallinity and can be polymerized by either light or heat. It is also effective to use a compound that can be crosslinked and / or at least a coating process, a pattern exposure process, a heating process, and an entire exposure process. In this case, after the entire surface exposure step, the film can be heated to a temperature higher than that at which the liquid crystal compound is polymerized and / or cross-linked, whereby the curing can be further advanced to form a stronger thin film.

As another means for obtaining the substrate on which the liquid crystal immobilization layer related to the present invention is formed, in the second manufacturing method, the coating process, the pattern exposure process, and the heating process are performed in the same manner, followed by the entire surface exposure process. Instead, a method of heating to a temperature higher than the isotropic phase transition temperature of the liquid crystal compound and higher than polymerization and / or crosslinking is also effective. In this case, in the two successive heating steps, first, the region not irradiated with light is transferred to an isotropic phase to be substantially non-oriented, and the region irradiated with an insufficient amount of light is irradiated with the region. Depending on the amount, the orientation of the remaining uncured component is disturbed and the region that has been irradiated with a sufficient amount of light in a low orientation state remains high while maintaining its orientation state without being disturbed by heating. It will be in an orientation state, and superposition | polymerization and / or bridge | crosslinking will continue, each maintaining that state then.

When the liquid crystal compound is maintained at a temperature higher than that maintained in the isotropic phase and the substrate is additionally exposed to polymerize and / or crosslink the liquid crystal compound, the pattern is formed in the previous step. It is also possible to perform light irradiation while adjusting the irradiation amount so that the portion other than the region where the light irradiation is performed with the maximum irradiation amount at the time of exposure is performed so as not to be overexposed.
Of course, such a method complicates the process compared with the case of performing the entire surface exposure, but if there is a concern that an unfavorable reaction may occur in the liquid crystal compound due to overexposure, the effect of suppressing it. It becomes an effective means.

As means for irradiating different amounts of light for each region, a method of performing a plurality of exposures using a plurality of photomasks, or performing a plurality of exposures while moving the same photomasks Method, a method using a halftone mask having a plurality of regions having different light transmittances, a method using a gray tone mask having a plurality of regions having slits less than the resolution of the exposure machine, and a light transmission wavelength A method using a wavelength limiting mask having a plurality of different regions, a method of drawing by scanning a light beam such as an electron beam, or a combination thereof is conceivable, but is not limited thereto, and only necessary for a desired region. Any method can be used as long as it can irradiate the light.

In any of the above-described plural types of manufacturing methods, the amount of light irradiation in pattern exposure is not necessarily directly proportional to the amount of birefringence. However, unlike methods that try to control the film thickness by developing after changing the dose, the region is formed without a so-called wet process such as a development process, so the same material is used. As long as the reproducibility of the birefringence expression amount with respect to the light irradiation amount is as high as possible, it is easy to find the conditions necessary for obtaining a desired phase difference, and stable production is not difficult.

Hereinafter, although an example is given and described about embodiment of this invention, this invention is not limited to these. Further, since the material used in the present invention is extremely sensitive to light, it is necessary to prevent exposure to unnecessary light such as natural light, and it goes without saying that all operations are performed under a yellow or red light. In the examples and comparative examples, “parts” means “parts by weight”.
First, the alkali development type coloring composition used for forming the color filter layer in the examples, the acrylic resin solution / pigment dispersion used therein, and the production of the salt milled pigment used as the raw material for the pigment dispersion are described. To do.

(Preparation of acrylic resin solution 1)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts n-Butyl methacrylate 55.0 parts 2-Hydroxyethyl methacrylate 15.0 parts 2,2′-azobisisobutyronitrile 4.0 parts After the reaction at 3 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. . The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution 1 was prepared.

(Preparation of acrylic resin solution 2)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts n-Butyl methacrylate 35.0 parts 2-Hydroxyethyl methacrylate 15.0 parts 2,2'-azobisisobutyronitrile 4.0 parts paracumylphenol ethylene oxide modification Acrylate 20.0 parts ("Aronix M110" manufactured by Toa Gosei Co., Ltd.)
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution 2 was prepared.

(Preparation of acrylic resin solution 3)
560 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 34.0 parts Methyl methacrylate 23.0 parts n-Butyl methacrylate 45.0 parts 2-Hydroxyethyl methacrylate 70.5 parts 2,2'-azobisisobutyronitrile 8.0 parts After completion of dropping, 100 more After reacting at 0 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain a copolymer solution. .
Next, with respect to 338 parts of the obtained copolymer solution, the mixture of the following compound was dripped at 70 degreeC over 3 hours.
2-Methacryloyl ethyl isocyanate 32.0 parts Dibutyltin laurate 0.4 parts Cyclohexanone 120.0 parts After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the nonvolatile content. Acrylic resin solution 3 was prepared by adding cyclohexanone to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The weight average molecular weight of the obtained acrylic resin was 20000, and the double bond equivalent was 470.

(Preparation of acrylic resin solution 4)
560 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 34.0 parts Methyl methacrylate 23.0 parts n-Butyl methacrylate 25.0 parts 2-Hydroxyethyl methacrylate 70.5 parts 2,2'-azobisisobutyronitrile 8.0 parts paracumylphenol ethylene oxide modification Acrylate 20.0 parts ("Aronix M110" manufactured by Toa Gosei Co., Ltd.)
After completion of the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A polymer solution was obtained.
Next, with respect to 338 parts of the obtained copolymer solution, the mixture of the following compound was dripped at 70 degreeC over 3 hours.
2-Methacryloyl ethyl isocyanate 32.0 parts Dibutyltin laurate 0.4 parts Cyclohexanone 120.0 parts After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the nonvolatile content. Acrylic resin solution 4 was prepared by adding cyclohexanone to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The weight average molecular weight of the obtained acrylic resin was 20000, and the double bond equivalent was 470.

(Manufacture of red salt milled pigment)
200 parts of red pigment (CI pigment red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (Inoue Manufacturing Co., Ltd.) And kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of “P.R.254 treated pigment” was obtained.

(Green salt milling pigment production example)
Except that the red pigment was replaced with a green pigment (CI pigment green 36, “Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), “PG 36” was produced in the same manner as in the production of the red salt milled pigment. A treated pigment "was obtained.
(Example of yellow salt milled pigment production)
Except that the red pigment was replaced with a yellow pigment (CI pigment yellow 138, “Lionol Yellow 1030” manufactured by Toyo Ink Manufacturing Co., Ltd.), “P.Y.138” was prepared in the same manner as in the production of the red salt milled pigment. A treated pigment "was obtained.
(Example of blue salt milled pigment production)
Except for the replacement of the red pigment with a blue pigment (CI pigment blue 15: 6, “Heliogen Blue L-6700F” manufactured by BASF), “P.B. 15: 6 treated pigment "was obtained.
(Purple salt milling pigment production example)
Except for the replacement of the red pigment with a purple pigment (CI pigment violet 23, “Lionogen Violet R6200” manufactured by Toyo Ink Manufacturing Co., Ltd.), “P.V. 23 treated pigment ".

(Production of red pigment dispersion)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a red pigment dispersion.
P. R. 254 treated pigment 10.0 parts Dispersing aid ("Solspers 20000" manufactured by Avicia) 1.0 part acrylic resin solution 1 34.0 parts cyclohexanone 55.0 parts

(Manufacture of green pigment dispersion)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a green pigment dispersion.
P. G. 36 treated pigments 10.0 parts dispersing aid ("Solsper's 20000" manufactured by Avicia) 1.0 parts acrylic resin solution 1 34.0 parts cyclohexanone 55.0 parts

(Manufacture of yellow pigment dispersion)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a yellow pigment dispersion.
P. Y. 138 treated pigment 10.0 parts Dispersing aid ("Solspers 20000" manufactured by Avicia) 1.0 part acrylic resin solution 1 34.0 parts cyclohexanone 55.0 parts

(Production of blue pigment dispersion)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a blue pigment dispersion.
P. B. 15: 6 treated pigment 10.0 parts dispersing aid ("BYK111" manufactured by Big Chemie) 1.0 part acrylic resin solution 2 34.0 parts cyclohexanone 55.0 parts

(Manufacture of purple pigment dispersion)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a blue pigment dispersion.
P. V. 23 treated pigment 10.0 parts dispersing aid ("BYK111" manufactured by Big Chemie) 1.0 part acrylic resin solution 2 34.0 parts cyclohexanone 55.0 parts

(Manufacture of red coloring composition 1)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali developing red coloring composition.
Red pigment dispersion 65.0 parts Acrylic resin solution 3 15.0 parts Trimethylolpropane triacrylate 3.5 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 part cyclohexanone 14.0 parts

(Manufacture of red coloring composition 2)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali developing red coloring composition.
Red pigment dispersion 33.0 parts Acrylic resin solution 3 45.0 parts Trimethylolpropane triacrylate 3.5 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 part cyclohexanone 16.0 parts

(Manufacture of green coloring composition 1)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali developing type green coloring composition.
Green pigment dispersion 53.0 parts Yellow pigment dispersion 32.0 parts Acrylic resin solution 3 3.0 parts Trimethylolpropane triacrylate 3.5 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 parts cyclohexanone 6.0 parts

(Manufacture of green coloring composition 2)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali developing type green coloring composition.
Green pigment dispersion 25.5 parts Yellow pigment dispersion 15.5 parts Acrylic resin solution 3 38.0 parts Trimethylolpropane triacrylate 3.5 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 parts cyclohexanone 15.0 parts

(Production of blue coloring composition 1)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali developing type blue coloring composition.
Blue pigment dispersion 45.0 parts Purple pigment dispersion 5.0 parts Acrylic resin solution 4 30.0 parts Trimethylolpropane triacrylate 3.5 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 part cyclohexanone 14.0 parts

(Production of blue coloring composition 2)
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali developing type blue coloring composition.
Blue pigment dispersion 22.5 parts Purple pigment dispersion 2.5 parts Acrylic resin solution 4 52.0 parts Trimethylolpropane triacrylate 3.5 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 part cyclohexanone 17.0 parts [Example 1]

(Formation of transmissive pixel)
After apply | coating the red coloring composition 1 obtained above with a spin coater, it heat-dried at 70 degreeC for 20 minute (s) in the clean oven, and obtained the application | coating board | substrate. After cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Further, baking was performed at 230 ° C. for 30 minutes in a clean oven to form a transmissive red pixel on the substrate. Next, the green colored composition 1 was used to form a transmissive green pixel, and the blue colored composition 1 was used to form a transmissive blue pixel. The film thickness of each color transmission portion pixel was 2.0 μm in all cases.
The color characteristics of the transmissive part pixels are shown in Table 1, and the spectral transmittance is shown in FIGS.

(Formation of reflective pixel)
After apply | coating the red coloring composition 2 obtained above with a spin coater, it heat-dried at 70 degreeC for 20 minute (s) in the clean oven, and obtained the application | coating board | substrate. After cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Further, baking was performed at 230 ° C. for 30 minutes in a clean oven to form a red reflection portion pixel on the substrate. Next, the green colored composition 2 was used to form a reflective portion green pixel, and the blue colored composition 2 was used to form a reflective portion blue pixel. The film thickness of each color reflection portion pixel was 2.0 μm in all cases.
The color characteristics of the reflective pixel are shown in Table 2, and the spectral transmittance is shown in FIGS.

(Formation of alignment film)
An alignment film material (“SE-1410” manufactured by Nissan Chemical Industries, Ltd.) is applied onto the color filter layer of the substrate with a spin coater so that the dry film thickness is 0.1 μm, and is heated on a hot plate at 90 ° C. And baked at 230 ° C. for 40 minutes in a clean oven. Subsequently, a rubbing process was performed on the substrate in a certain direction to obtain a substrate having orientation ability.

(Phase difference thin film process (a))
A liquid crystal compound obtained by stirring and mixing a mixture having the following composition and filtering through a 0.6 μm filter is 1.6 μm in dry thickness on a spin coater on the alignment film of the substrate. And then dried by heating at 90 ° C. for 2 minutes on a hot plate to obtain a liquid crystal alignment substrate.
Horizontally-aligned polymerizable liquid crystal 39.7 parts ("Palocolor LC 242" manufactured by BASF Japan Ltd.)
Photopolymerization initiator 0.3 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 6.0 parts ("BYK330" 2% cyclohexanone solution manufactured by Big Chemie)
Cyclohexanone 154.0 parts

(Phase difference thin film process (b))
Next, the liquid crystal alignment substrate was exposed to ultraviolet rays for each color region of the reflection portion through a photomask using an ultrahigh pressure mercury lamp. The amount of UV irradiation was 500 mJ / cm 2 in the reflective red pixel region, 200 mJ / cm 2 in the reflective green pixel region, and 5 mJ / cm 2 in the reflective blue pixel region. Each color region of the transmission part was not exposed.

(Phase difference thin film process (c) and (d))
Subsequently, the substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to obtain a color filter substrate with a retardation film.
When the optical anisotropy of each color region of the color filter substrate was measured, the reflection portion red pixel region was found to have a birefringence (hereinafter simply referred to as birefringence) of the retardation film obtained by calculation with an in-plane retardation of 160 nm in light having a wavelength of 630 nm. Is 0.101, the reflection part green pixel region has an in-plane phase difference of 137 nm and a birefringence of 0.087 for light with a wavelength of 535 nm, and the reflection unit blue pixel region has a wavelength of 115 nm for light with a wavelength of 450 nm and the birefringence is 0.075. In the transmissive part pixel, almost no phase difference was recognized in each color region. The results are shown in Table 3.

(Production of liquid crystal display device)
A transparent indium tin oxide (ITO) electrode layer is formed on the obtained color filter substrate, a resin columnar spacer is formed so that the cell gap is ½ wavelength, and a columnar spacer is formed in each color reflection pixel region. After forming the cell gap adjusting layer so as to be a half film thickness, a polyimide alignment layer was formed thereon. On the other hand, a reflective layer is formed in a region corresponding to the reflective pixel of the color filter substrate on one surface of another (second) glass substrate, and a TFT array and a pixel electrode are formed. A layer was formed to obtain a TFT array substrate.
Of the two substrates prepared in this way, an acrylic epoxy adhesive mixed with spacer particles is applied to the outer periphery of the polyimide alignment layer forming surface of the color filter substrate with a seal coating device, and the region surrounded by the adhesive A vertically aligned nematic liquid crystal having a negative dielectric anisotropy was dropped on the liquid crystal. Then, after aligning the color filter substrate and the TFT array substrate in a vacuum of about 1 Pa so that the alignment layers face each other, ultraviolet rays are irradiated to cure the adhesive, A liquid crystal cell is obtained by baking for a period of time, and between this pair of direct-current Nicol polarizing plates, the pretwist angle of the liquid crystal layer and the slow axis of the retardation film are 45 ° with respect to the absorption axis of the polarizing plate. A liquid crystal display device was obtained in combination with a backlight unit.
The obtained liquid crystal display device is bright white when the backlight is turned on and a voltage is applied (transparent white display), and is tightened when the backlight is turned on and no voltage is applied (transparent black display). Black was observed. In addition, under illumination light, when the voltage is applied without turning on the backlight (reflected white display), white with no color is displayed, while when the backlight is not turned on and voltage is not applied (transparent black display), the colored is displayed. No black was observed.
[Example 2]

(Formation of transmissive pixel)
Similarly to Example 1, a transmissive portion red pixel, a transmissive portion green pixel, and a transmissive portion blue pixel were formed on a glass substrate. The film thickness of each color transmission pixel was 2.0 μm in all the same manner as in Example 1, and the color characteristics were almost the same.

(Formation of reflective pixel)
The red coloring composition 1 obtained above was applied by a spin coater so as to be thinner than a transmissive pixel, and then heat-dried at 70 ° C. for 20 minutes in a clean oven to obtain a coated substrate. After cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Further, baking was performed at 230 ° C. for 30 minutes in a clean oven to form a red reflection portion pixel on the substrate. Next, a green pixel was similarly formed using the green coloring composition 2, and further a blue pixel was formed using the blue coloring composition 2. The film thickness of each color reflection pixel was 1.0 μm in all cases.
The color characteristics of the reflective pixel are shown in Table 4, and the spectral transmittance is shown in FIGS.

(Phase difference thin film process (a))
After forming the color filter layer, the liquid crystal compound obtained by stirring and mixing the mixture having the following composition to be uniform and filtering through a 0.6 μm filter is dried on the color filter layer of the substrate by a spin coater. The film was applied to a thickness of 3.3 μm, and dried by heating on a hot plate at 90 ° C. for 2 minutes to obtain a liquid crystal alignment substrate.
Horizontally-aligned polymerizable liquid crystal 19.1 parts (“UCL-018” manufactured by Dainippon Ink & Chemicals, Inc.)
0.9 parts of photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 3.0 parts ("BYK330" 2% cyclohexanone solution manufactured by Big Chemie)
77.0 parts of cyclohexanone

(Phase difference thin film process (b))
Next, the liquid crystal alignment substrate was exposed to ultraviolet rays for each color region through a photomask using an ultrahigh pressure mercury lamp. The amount of ultraviolet irradiation was 500 mJ / cm 2 in the red pixel region, 30 mJ / cm 2 in the green pixel region, and 10 mJ / cm 2 in the blue pixel region.

(Phase difference thin film process (c) and (d))
Subsequently, while maintaining the substrate at 80 ° C. with a hot plate in a nitrogen atmosphere, the entire surface of the substrate was exposed to ultraviolet rays using an ultra-high pressure mercury lamp to obtain a color filter substrate with a retardation film.
When the optical anisotropy of each color region of the color filter substrate was measured, the reflection portion red pixel region had an in-plane phase difference of 160 nm and birefringence of 0.101 for light having a wavelength of 630 nm, and the reflection portion green pixel region had a wavelength of 535 nm. The birefringence was 0.087 at an in-plane phase difference of 137 nm, and the blue pixel region of the reflecting portion was 115 nm and the birefringence was 0.075 for light having a wavelength of 450 nm. In the transmissive part pixel, almost no phase difference was recognized in each color region. The results are shown in Table 5.

(Production of liquid crystal display device)
In the same manner as in Example 1, necessary steps were performed on the obtained color filter substrate, a TFT array substrate was prepared, and both substrates were bonded to obtain a liquid crystal cell. This liquid crystal cell was arranged in the same manner between one set of polarizing Nicol polarizing plates, and a liquid crystal display device was manufactured in combination with a backlight unit.
The obtained liquid crystal display device is bright white when the backlight is turned on and a voltage is applied (transparent white display), and is tightened when the backlight is turned on and no voltage is applied (transparent black display). Black was observed. In addition, under illumination light, when the voltage is applied without turning on the backlight (reflected white display), white with no color is displayed, while when the backlight is not turned on and voltage is not applied (transparent black display), the colored is displayed. No black was observed.
[Comparative Example 1]

(Formation of transparent pixels)
Similarly to Example 1, a transmissive portion red pixel, a transmissive portion green pixel, and a transmissive portion blue pixel were formed on a glass substrate. The film thickness of each color transmission pixel was 2.0 μm in all the same manner as in Example 1, and the color characteristics were almost the same.

(Formation of reflective pixels)
In the same manner as in Example 1, a reflective portion red pixel, a reflective portion green pixel, and a reflective portion blue pixel were formed on a glass substrate. The film thickness of each color transmission pixel was 2.0 μm in all the same manner as in Example 1, and the color characteristics were almost the same.

(Formation of alignment film)
In the same manner as in Example 1, an alignment film material was applied on the color filter layer of the substrate, and then this substrate was rubbed to obtain a substrate having alignment ability.

(Phase difference thin film process (a))
A liquid crystal compound having the same composition as in Example 1 was applied on the alignment film of the substrate with a spin coater so as to have a dry film thickness of 1.3 μm, and dried by heating at 90 ° C. for 2 minutes on a hot plate. An alignment substrate was obtained.

(Phase difference thin film process (b))
Next, the liquid crystal alignment substrate was exposed to ultraviolet rays for each color region of the reflection portion through a photomask using an ultrahigh pressure mercury lamp. The amount of ultraviolet irradiation was 500 mJ / cm 2 for each color region of the reflecting portion. Each color region of the transmission part was not exposed.

(Phase difference thin film process (c) and (d))
Subsequently, the substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to obtain a color filter substrate with a retardation film.
When the optical anisotropy of each color region of the color filter substrate was measured, the reflection portion red pixel region had an in-plane retardation of 131 nm and birefringence of 0.099 for light having a wavelength of 630 nm, and the reflection portion green pixel region had a wavelength of 535 nm. The birefringence was 0.103 at an in-plane phase difference of 137 nm, and the blue pixel region of the reflective portion was 149 nm and the birefringence was 0.113 for light having a wavelength of 450 nm. Note that the in-plane phase difference differs for each color pixel due to the refractive index wavelength dispersion characteristics of the material. In the transmissive part pixel, almost no phase difference was recognized in each color region. The results are shown in Table 6.

(Production of liquid crystal display device)
In the same manner as in Example 1, necessary steps were performed on the obtained color filter substrate, a TFT array substrate was prepared, and both substrates were bonded to obtain a liquid crystal cell. This liquid crystal cell was arranged in the same manner between one set of polarizing Nicol polarizing plates, and a liquid crystal display device was manufactured in combination with a backlight unit.
The obtained liquid crystal display device has good display quality in the state where the voltage is applied (transparent white display) and the state where no voltage is applied (transparent black display) in the state where the backlight is turned on, as in the first embodiment. However, when the voltage was applied without lighting the backlight (illuminated white display) under the illumination light, the white colored slightly green did not light the backlight and no voltage was applied (transmission black) In the display), a black colored magenta was observed.
[Example of simulation]

Hereinafter, although the example of an optical calculation result is given and described about the effect of the present invention, the desirable composition of the present invention is not restricted to these.
First, conditions commonly set for calculation will be described.

(Common conditions-Polarizing plate)
The transmittance of the polarizing plate alone is 40.24% at a wavelength of 450 nm, 43.52% at a wavelength of 535 nm, 43.95% at a wavelength of 630 nm, and the transmittance when two transmission axes are arranged in parallel is a wavelength of 450 nm. 32.19% at a wavelength of 535 nm, 37.57% at a wavelength of 535 nm, 38.28% at a wavelength of 630 nm, and the transmittance when two transmission axes are orthogonally arranged are 0.015% at a wavelength of 450 nm and 0.004% at a wavelength of 535 nm. Assuming 0.001% at a wavelength of 630 nm. The refractive index was 1.51 regardless of the wavelength, and the thickness was 180 μm. The spectral transmittance of the polarizing plate is shown in FIGS.

(Common conditions-glass substrate)
The glass substrate was assumed to have a refractive index of 1.5 and a transmittance of 100% regardless of the wavelength. The thickness was 0.7 mm.

(Common conditions-color filter)
The color filter layer has the spectral transmittance when the red colored composition 2, the green colored composition 2 and the blue colored composition 2 obtained in the example are formed with a thickness of 2 μm for the reflective pixel, and the transmissive pixel. Similarly, the spectral transmittance when the red coloring composition 1, the green coloring composition 1, and the blue coloring composition 1 were formed at a thickness of 2 μm was employed. Regardless of the wavelength, the refractive index was 1.7, and the thickness was 2.0 μm. Table 7 shows the color characteristics of the color filter.

(Common conditions-Liquid crystal layer)
The liquid crystal has a refractive index in the major axis direction of 1.60 regardless of wavelength, a refractive index in the minor axis direction of 1.50 regardless of wavelength, an elastic constant of 13.2 pN (spread), 6.5 pN (twist), It was assumed that the dielectric constant in the major axis direction was 3.1 and the dielectric constant in the minor axis direction was 8.3. The pretilt angle was 89 °.

(Common conditions-retardation film)
The retardation film is a uniaxial optically anisotropic element having an in-plane retardation, and an average refractive index of 1.567 at a wavelength of 450 nm, 1.553 at a wavelength of 535 nm, 1.546 at a wavelength of 630 nm, and transmittance. Was assumed to be 100% regardless of wavelength.

(Common conditions-Display device configuration)
The layer configuration was such that the reflective pixel was a polarizing plate / glass substrate / color filter layer / retardation thin film / liquid crystal layer / specular reflector from the viewing side, and the thickness of the liquid crystal layer was 1.5 μm. The transmissive part pixels were polarizing plate / glass substrate / color filter layer / retardation thin film / liquid crystal layer / glass substrate / polarizing plate from the viewing side, and the thickness of the liquid crystal layer was 3.0 μm. The thickness of the retardation film is set so that a quarter (133.75 μm) of the center wavelength (535 nm) can be obtained approximately for each green pixel in the reflection portion in each calculation. The thickness was the same. In the polarizing plate, the absorption axis on the viewing side was 0 °, the absorption axis on the backlight side was 90 °, the pretwist angle of the liquid crystal layer and the slow axis of the retardation film were 45 °.
When the voltage applied to the liquid crystal layer was 0 V, black display was obtained, and when 5 V was white display, the spectral transmittance in the front direction was obtained, and the contrast was calculated using the light source as the C light source. Note that reflection at the interface other than the specular reflector is not considered.

[Simulation Example 1]
For the retardation film, the film thickness is 1.55 μm, and the birefringence is 0.101 for the reflective red pixel, 0.086 for the reflective green pixel, 0.074 for the reflective blue pixel, and 3.0 for the transmissive pixel. Optical calculation was performed with × 10 ⁻⁴ . The contrast was 67 at the reflection part and 8470 at the transmission part. Table 8 shows the setting characteristics of the phase difference thin film, and FIG. 13 shows the reflectance of the reflective portion white display and black display.

[Simulation Example 2]
Regarding the retardation film, the film thickness is 1.51 μm, and the birefringence is 0.101 for the reflection portion red pixel, 0.089 for the reflection portion green pixel, 0.079 for the reflection portion blue pixel, and 5.0 for the transmission portion pixel. Optical calculation was performed with × 10 ⁻⁴ . The contrast was 82 at the reflection part and 7580 at the transmission part. Table 9 shows the setting characteristics of the retardation film, and FIG. 14 shows the reflectance of the reflective portion white display and black display.

[Simulation Example 3]
As for the retardation film, the film thickness is 1.45 μm, and the birefringence is 0.101 for the reflection portion red pixel, 0.092 for the reflection portion green pixel, 0.084 for the reflection portion blue pixel, and 7.0 for the transmission portion pixel. Optical calculation was performed with × 10 ⁻⁴ . The contrast was 80 at the reflection part and 6700 at the transmission part. Table 10 shows the setting characteristics of the phase difference thin film, and FIG. 15 shows the reflectance of the reflective portion white display and black display.

[Simulation Example 4]
Regarding the retardation film, the film thickness is 1.41 μm, and the birefringence is 0.101 for the reflection portion red pixel, 0.095 for the reflection portion green pixel, 0.089 for the reflection portion blue pixel, and 9.0 for the transmission portion pixel. Optical calculation was performed with × 10 ⁻⁴ . The contrast was 76 at the reflection part and 5880 at the transmission part. Table 11 shows the setting characteristics of the retardation film, and FIG. 16 shows the reflectivity of the reflective portion white display and black display.

[Simulation Example 5]
Regarding the retardation film, the film thickness is 1.37 μm, and the birefringence is 0.101 for the reflection portion red pixel, 0.098 for the reflection portion green pixel, 0.094 for the reflection portion blue pixel, and 1.1 for the transmission portion pixel. Optical calculation was performed with × 10 ⁻³ . The contrast was 64 at the reflection part and 5160 at the transmission part. Table 12 shows the setting characteristics of the retardation film, and FIG. 17 shows the reflectance of the reflective portion white display and black display.

[Simulation comparison example]
Regarding the retardation film, the film thickness is 1.31 μm, and the birefringence is 0.099 for the reflection part red pixel, 0.103 for the reflection part green pixel, 0.113 for the reflection part blue pixel, and 3.0 for the transmission part pixel. Optical calculation was performed with × 10 ⁻³ . The contrast was 32 at the reflection part and 1510 at the transmission part. Table 13 shows the setting characteristics of the phase difference thin film, and FIG. 18 shows the reflectivity of the reflective portion white display and black display.

(simulation result)
As described above, as shown in the simulation example, when Δn [fr] / λd [fr] of the retardation film is 0.75 or more and 1.35 or less in the reflection portion pixel, the contrast is approximately 60 to 80. . When the birefringence of the retardation film is less than 1.2 × 10 ⁻³ in the transmissive part pixel, a contrast of 5000 or more was obtained. On the other hand, when the minimum value of Δn [fr] / λd [fr] of the retardation film is 0.626 and the maximum value is 1.598 in the reflection portion pixel, as shown in the simulation comparative example, the contrast is 32 and the transmission is transmitted. When the birefringence of the retardation film was 3.0 × 10 ^{−3 in} the ^partial pixels, the contrast was more than 1500. Table 14 shows the relationship between Δn [fr] / λd [fr] and the contrast in the reflection unit pixel, and the relationship between the birefringence and the contrast in the transmission unit pixel.

Spectral transmittance of the red pixel of the transmissive part obtained from the red coloring composition 1 Spectral transmittance of green pixel of transmissive part obtained from green coloring composition 1 Spectral transmittance of blue pixel of transmissive part obtained from blue coloring composition 1 Spectral transmittance of reflection portion red pixel obtained from red coloring composition 2 Spectral transmittance of green pixel of reflection part obtained from green coloring composition 2 Spectral transmittance of blue pixel of reflection part obtained from blue coloring composition 2 Spectral transmittance of red pixel of reflection part obtained from red coloring composition 1 Spectral transmittance of the reflective portion green pixel obtained from the green coloring composition 1 Spectral transmittance of blue pixel of reflection part obtained from blue coloring composition 1 Spectral transmittance of polarizing plate alone Spectral transmittance when two polarizing plates are arranged in parallel Spectral transmittance when two polarizing plates are arranged orthogonally Reflector white display and black display reflectivity Reflector white display and black display reflectivity Reflector white display and black display reflectivity Reflector white display and black display reflectivity Reflector white display and black display reflectivity Reflector white display and black display reflectivity Schematic about an example of the color filter used for the liquid crystal display device of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter substrate 2 ... Glass substrate 3 ... Color filter layer 4 ... Liquid crystal fixed layer (retardation thin film)
4a ... region R
4b ... Region G
4c region B
4d ... area W

Claims (12)

At least a first substrate;
A second substrate facing the first substrate;
A first polarizing plate disposed on the opposite side of the first substrate of both sides of the first substrate;
A second polarizing plate disposed on the opposite side of the first substrate of both surfaces of the second substrate so that the absorption axis direction is 90 ° different from that of the first polarizing plate;
A liquid crystal layer sandwiched between the first substrate and the second substrate;
A liquid crystal display device in which a color filter layer is provided between the first substrate and the liquid crystal layer,
The color filter layer is composed of a large number of pixels of two or more colors, and each pixel includes a reflection part and a transmission part,
A retardation film comprising a liquid crystal immobilization layer is provided between the first substrate and the second substrate,
The retardation thin film has a birefringence of at least one layer of the pixels due to a difference in the degree of orientation of the liquid crystal fixing layer for each color and / or a region corresponding to the reflection part / transmission part. The in-plane birefringence satisfying the formula (1) in the region corresponding to the reflective portion of the pixel and the formula (2) in the region corresponding to the transmissive portion of the pixel. The liquid crystal display device according to claim 1.
(1) 0.75 ≦ Δn [fr] / λd [fr] ≦ 1.35
(Where λd [fr] = (d [f1] × λ [f2]) / (d [f2] × λ [f1]))
(2) Δn [t] <1.2 × 10 ⁻³
(Where Δn [t] is the in-plane birefringence in the region corresponding to the pixel transmitting portion, and Δn [fr] is the in-plane birefringence in the region corresponding to the pixel reflecting portion of a certain color (hereinafter referred to as color 1). Is the ratio of the in-plane birefringence in the region corresponding to the pixel reflection portion of any other color (hereinafter color 2), and d [f1] and d [f2] are the pixel reflections of color 1 and color 2, respectively. The thickness of the retardation layer in the region corresponding to the part, λ [f1] · λ [f2] is the center wavelength of the color of the pixel reflection part of color 1 and color 2, respectively. The liquid crystal display device according to claim 1, wherein the retardation film having the in-plane birefringence has substantially the same slow axis direction in any region. 3. The liquid crystal sandwiched between the first substrate and the second substrate is aligned substantially perpendicular to the two substrates when no voltage is applied. The liquid crystal display device described. The liquid crystal display device according to claim 1, wherein the retardation film is formed by polymerizing and / or crosslinking a compound containing a thermotropic liquid crystal. In the manufacturing method of the liquid crystal display device according to claim 1, at least
(A) A state in which a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or cross-linked by light is applied onto the first substrate, and the liquid crystal compound is aligned in a predetermined direction. Forming a thin film of
(B) irradiating the first substrate with light so as to have a different irradiation amount for each region corresponding to a predetermined pattern of each color of the color filter;
(C) heating the first substrate to a temperature equal to or higher than the isotropic phase transition temperature of the liquid crystal compound;
(D) exposing the entire surface of the first substrate while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase;
(E) making the first substrate and the second substrate face each other and enclosing a liquid crystal compound;
The manufacturing method of the liquid crystal display device with a phase difference thin film characterized by including these. (A) A solution containing a compound that exhibits thermotropic liquid crystallinity and that can be polymerized and / or cross-linked by light is applied onto the first substrate, and the liquid crystal compound is aligned in a predetermined direction. 6. The method of manufacturing a liquid crystal display device according to claim 5, wherein the step of forming a thin film in a state is performed so that the thickness of the thin film is uniform over the entire substrate. (A) A solution containing a compound that exhibits thermotropic liquid crystallinity and that can be polymerized and / or cross-linked by light is applied onto the first substrate, and the liquid crystal compound is aligned in a predetermined direction. Forming a thin film in a state,
On the first substrate, a solution containing a compound having thermotropic liquid crystallinity and capable of being polymerized and / or cross-linked by either light or heat was applied, and the liquid crystal compound was aligned in a predetermined direction. Forming a thin film in a state, and
(D) a step of exposing the entire surface of the first substrate while maintaining the temperature at which the liquid crystal compound is maintained in an isotropic phase;
7. The step of heating the first substrate to a temperature not lower than the isotropic phase transition temperature of the liquid crystal compound and higher than polymerization and / or crosslinking. A method for producing a liquid crystal display device according to claim 1. (D) a step of exposing the entire surface of the first substrate while maintaining the temperature at which the liquid crystal compound is maintained in an isotropic phase;
While maintaining the first substrate at a temperature higher than that at which the liquid crystal compound is kept in an isotropic phase, light irradiation is performed on portions other than the region irradiated with light at the maximum irradiation amount in the step (b). The method of manufacturing a liquid crystal display device according to claim 5, wherein: 9. The amount of irradiation when performing light irradiation while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase according to claim 8, including the light irradiation in the step (b) in each region. The method for manufacturing a liquid crystal display device is characterized in that the exposure amount is the same as the exposure amount of the region irradiated with light at the maximum irradiation amount in the step (b). The method for manufacturing a liquid crystal display device according to claim 5, wherein a color filter layer is formed on the first substrate before the step (a) is performed. The method for manufacturing a liquid crystal display device according to claim 5, wherein a color filter layer is formed on the first substrate after performing the step (d). The steps (a) to (d) applied to the first substrate are all applied to the second substrate, and a TFT layer is formed on the second substrate before performing the step (a). The method for manufacturing a liquid crystal display device according to claim 5, further comprising a step of:

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