JP2009080495A - Retardation substrate and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a retardation substrate having optical compensation ability capable of dissolving a problem of retardation produced when performing a multi-color display by using a liquid crystal display device, and to provide a method of manufacturing the retardation substrate easily with high quality. <P>SOLUTION: The retardation substrate includes at least a substrate and a fixed liquid crystal layer disposed on the substrate, wherein the fixed liquid crystal layer has optical anisotropy and is disposed so as to have different birefringence every a plurality of areas, due to the different degree of alignment. <P>COPYRIGHT: (C)2009,JPO&INPIT

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 color filter substrate that can be suitably used for a matrix type color liquid crystal display device incorporated and used in a flat-type 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. .
On the other hand, a liquid crystal display device for television use is often applied by combining a retardation film and a linear polarizing plate in order to further improve visibility in all directions and the like.

  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 a retardation amount of λ / 4 (about 138 nm) 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 region (center wavelength around 450 nm) is more than λ / 4, and the red wavelength region (center wavelength around 630 nm) is insufficient relative to λ / 4, and red and blue display pixels. In this case, complete circularly polarized light cannot be obtained.

In addition, when a retardation film is designed so that the phase difference is compensated for one of the three colors RGB (wavelength region) in a liquid crystal display device for television applications, compensation is not possible for the other colors (wavelength region). Often there will be completeness. The following factors can be cited as the cause.
(1) The liquid crystal of the cell does not necessarily have the same retardation value in the entire wavelength region,
(2) Many of the color pigments used in color filters have optical anisotropy,
(3) Furthermore, since the degree is different depending on the type of pigment, the phase difference varies depending on the red, green, and blue pixels.

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

A configuration of the present invention for solving the above-described problems will be described below.
(Claim 1)
In a retardation substrate including at least a substrate and a liquid crystal fixing layer provided on the substrate,
The liquid crystal immobilization layer has optical anisotropy, and the liquid crystal immobilization layer is provided so that the birefringence is different for each of a plurality of regions due to different degrees of orientation. A characteristic retardation substrate.
(Claim 2)
In a retardation substrate including at least a substrate and a liquid crystal fixing layer provided on the substrate,
The liquid crystal immobilization layer has optical anisotropy, and the liquid crystal immobilization layer is continuously provided so that the birefringence is different for each of a plurality of regions due to different degrees of orientation. A retardation substrate, which is a film.
(Claim 3)
A retardation substrate comprising at least a substrate and a liquid crystal immobilization layer, which is produced from a production method including the following steps.
(A) A thin film in which the liquid crystal compound is aligned in a predetermined direction is formed on a substrate by applying a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or crosslinked by light. The process of
(B) a step of irradiating the substrate with light so as to have a different dose for each region;
(C) A step of heating the liquid crystal compound to an isotropic phase transition temperature or higher to form a liquid crystal immobilization layer.
(D) A step of curing an uncured liquid crystal compound to form a liquid crystal immobilization layer.
(Claim 4)
A retardation substrate comprising at least a substrate and a liquid crystal immobilization layer, which is produced from a production method including the following steps.
(A) A thin film in which the liquid crystal compound is aligned in a predetermined direction is formed on a substrate by applying a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or crosslinked by light. The process of
(B) a step of irradiating the substrate with light so as to have a different dose for each region;
(C) heating the liquid crystal compound to an isotropic phase transition temperature or higher;
(D) A step of exposing the entire surface of the substrate while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase to form a liquid crystal fixed layer.
(Claim 5)
3. The retardation substrate according to claim 1, wherein the liquid crystal fixing layer is formed by polymerizing and / or crosslinking a compound containing a thermotropic liquid crystal. 4.
(Claim 6)
The retardation substrate according to claim 1, wherein any one of glass, plastic, and film substrate is used as the substrate.
(Claim 7)
2. The liquid crystal fixing layer according to claim 1, wherein the phase difference has a predetermined value for each color so as to optically compensate the incident light transmitted through the color filter for each color. The phase difference substrate for a color filter according to any one of 6.
(Claim 8)
The retardation substrate according to claim 1, wherein the liquid crystal fixing layer has a uniform thickness.
(Claim 9)
The retardation substrate according to claim 1, wherein a TFT is provided between the liquid crystal fixing layer and the substrate.
(Claim 10)
The retardation substrate according to claim 1, further comprising a TFT provided on the liquid crystal immobilization layer.
(Claim 11)
A liquid crystal display device using the retardation substrate according to claim 1.

[Configurations related to the present invention other than the above]
(Other configuration 1)
An optical element comprising at least a substrate and a liquid crystal fixing layer provided on the substrate, wherein the liquid crystal compound layer has optical anisotropy and is optically compensated by the liquid crystal fixing layer. .
(Other configuration 2)
In the above, the liquid crystal fixing layer has an optical element whose phase difference has a predetermined value for each color so as to optically compensate the incident light for each color.
(Other configuration 3)
In the above, the liquid crystal fixing layer is provided so as to have different birefringence due to different degrees of orientation for each color.
(Other configuration 4)
In the above, the liquid crystal immobilization layer is formed by polymerizing and / or crosslinking a compound containing a thermotropic liquid crystal.
(Other configuration 5)
In the above, the optical element is any one of a glass substrate, a film substrate, and a TFT substrate.
(Other configuration 6)
In a method for manufacturing an optical element including a substrate and a liquid crystal immobilization layer provided on the substrate, at least,
(A) A thin film in which the liquid crystal compound is aligned in a predetermined direction is formed on a substrate by applying a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or cross-linked by light. And a process of
(B) irradiating the substrate with light so as to have a different dose for each region corresponding to a predetermined pattern of each color of the optical element;
(C) heating the substrate above the isotropic phase transition temperature of the liquid crystal compound;
(D) a step of exposing the entire surface of the substrate while maintaining the temperature at which the liquid crystal compound is maintained in an isotropic phase;
The manufacturing method of the optical element characterized by the above-mentioned.
(Other configuration 7)
In the above (Other Configuration 6), 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 substrate (a), and the liquid crystal compound has a predetermined structure. A method of manufacturing an optical element, wherein the step of forming a thin film oriented in a direction is performed so that the thickness of the thin film is uniform over the entire substrate.
(Other configuration 8)
In the above (Other Configuration 6) or (Other Configuration 7), a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or crosslinked at least by light is applied onto the substrate (a). And forming a thin film in which the liquid crystal compound is aligned in a predetermined direction,
A thin film in which a solution containing a compound having a thermotropic liquid crystallinity and capable of being polymerized and / or crosslinked by light or heat is applied to the substrate, and the liquid crystal compound is oriented in a predetermined direction. Forming a process, and
(D) a step of exposing the entire surface of the substrate while maintaining the temperature at which the liquid crystal compound is maintained in an isotropic phase;
A method for producing an optical element, characterized in that the substrate is heated to a temperature equal to or higher than an isotropic phase transition temperature of the liquid crystal compound and higher than polymerization and / or crosslinking.
(Other configuration 9)
In (Other Configuration 6) or (Other Configuration 7), (d) a step of exposing the entire surface while maintaining the substrate at a temperature higher than the liquid crystal compound is kept in an isotropic phase,
A step of performing light irradiation on a portion other than the region irradiated with light at the maximum irradiation amount in the step (b) while maintaining the substrate at a temperature higher than that at which the liquid crystal compound is kept in an isotropic phase. The method of manufacturing an optical element according to claim 6, wherein:
(Other configuration 10)
In the above (other configuration 9), the irradiation amount when performing light irradiation while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase is set in each region, and the light irradiation in the step (b) is performed. The total exposure amount including the same is performed so as to be the same as the exposure amount of the region irradiated with light at the maximum irradiation amount in the step (b).
(Other configuration 11)
In the above (Other Configuration 6) to (Other Configuration 10), a TFT layer is formed on the substrate before performing the step (a).
(Other configuration 12)
In the above (other configuration 6) to (other configuration 10), a TFT layer is formed on a substrate after the step (d) is performed.
(Other configuration 13)
In a color filter substrate having at least a substrate and a color filter layer provided on the substrate,
The color filter layer is composed of a large number of display pixels of two or more colors;
A liquid crystal immobilization layer is provided on the color filter layer,
The liquid crystal fixed layer has optical anisotropy, and is optically compensated by the liquid crystal fixed layer,
The color filter substrate according to claim 1, wherein the liquid crystal fixing layer is provided so that the birefringence is different due to the degree of orientation being different for each color.
(Other configuration 14)
In a color filter substrate having at least a substrate and a color filter layer provided on the substrate,
The color filter layer is composed of a large number of display pixels of two or more colors;
A liquid crystal immobilization layer is provided between the color filter layer and the substrate,
The liquid crystal fixed layer has optical anisotropy, and is optically compensated by the liquid crystal fixed layer,
The color filter substrate according to claim 1, wherein the liquid crystal fixing layer is provided so that the birefringence is different due to the degree of orientation being different for each color.
(Other configuration 15)
The color filter substrate as described above, wherein the liquid crystal immobilization layer is formed by polymerizing and / or crosslinking a compound containing a thermotropic liquid crystal.
(Other configuration 16)
The retardation substrate as described above, wherein the liquid crystal immobilization layer has a uniform thickness.
(Other configuration 17)
A liquid crystal display device using the color filter substrate.

According to the present invention, in the retardation substrate, the retardation problem, which was the above problem, can be solved without separately providing a retardation film or the like.
Further, even in a multicolor color filter, since optical compensation can be performed for each color, the problem caused by the phase difference can be solved.
Further, since the liquid crystal compound layer is provided so that the birefringence is different due to the degree of orientation being different for each color, even if the thickness of the liquid crystal immobilization layer remains uniform, Optimum phase difference compensation can be performed for each color, and the above phase difference problem can be solved.
According to the present invention, since the thermotropic liquid crystal is used for the liquid crystal immobilization layer, a retardation substrate having different anisotropy for each color of light passing through the above-described anisotropy can be manufactured using heat treatment. It was.
According to the present invention, it is possible to manufacture a retardation substrate that facilitates the process by making the film thickness uniform.
According to the present invention, it is possible to provide a liquid crystal display device in which the above-described problem of phase difference is reduced.

The substrate of the present invention on which a thin film formed by polymerizing and / or crosslinking a solution containing a compound exhibiting liquid crystallinity is described. Such a substrate can be used not only as a color filter substrate but also as a self-holding retardation substrate and retardation film. Examples of the substrate include glass, plastic, and film base material.
Hereinafter, a retardation substrate with a color filter in which a liquid crystal compound layer is formed by laminating the liquid crystal compound on a color filter substrate on which display pixels are formed or on a light-transmitting film such as plastic will be described as an example. .

  FIG. 1 illustrates one form (part) of a color filter substrate obtained by 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.

  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 of 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.

  Since the color filter substrate 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, in the region having a separate phase difference amount. 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 the color filter substrate of the present invention are conceivable. However, as a method for forming the color filter layer, an existing method for producing a color filter can be used. When the color filter layer is directly provided on the substrate, the color filter layer may be provided further on the liquid crystal fixing layer provided on the substrate.
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 of the present invention includes a plurality of color display pixels formed on a planar 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, the liquid crystal immobilization layer of the present invention may be formed on the planar body.

  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 of 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 and derivatives thereof , Line It can be mentioned 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 color filter substrate of the present invention is incorporated in a matrix type liquid crystal display device, the planar body is a glass plate or a resin plate, or display pixels are formed on them. A light-transmitting substrate such as a color filter is suitable. In addition, a light-transmitting film such as a plastic film can be used as the planar body. When a liquid crystal immobilization layer is formed on a flat body that is not provided with a color filter layer, the color filter layer is usually formed in a subsequent process. As shown in Fig. 4, by adopting a configuration in which a liquid crystal fixing layer is provided on a flat body and no color filter layer is provided, or a configuration in which a liquid crystal fixing layer is provided on a TFT substrate, the color filter process is not performed. It is also possible to manufacture a product such as a substrate or a film that satisfies the spirit of the present invention.

  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 the color filter substrate of the present invention, the liquid crystal used in the liquid crystal solution is a compound which exhibits thermotropic liquid crystallinity and can be polymerized and / or crosslinked by light or heat, Similarly, a method in which at least a coating process, a pattern exposure process, a heating process, and an entire exposure process are performed is also effective. 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 color filter substrate of the present invention, in the second production method, the coating step, the pattern exposure step, and the heating step are performed in the same manner. A method of heating to a temperature higher than the isotropic phase transition temperature 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 performing the exposure is not excessive.
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, embodiments of the present invention will be described with respect to an example in which a color filter is added to a retardation substrate composed of a substrate and a liquid crystal fixing layer to form a color filter substrate, but the present invention is not limited thereto. is not. 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 completion of dropping, further 80 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 Paracmylphenol 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, further 100 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 to 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 Paracmylphenol 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 to 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 8.0 parts Dispersing aid ("Solspers 20000" manufactured by Avicia) 1.0 part Acrylic resin solution 1 40.0 parts Cyclohexanone 51.0 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 8.0 parts Dispersing aid ("Solspers 20000" manufactured by Avicia) 1.0 parts Acrylic resin solution 1 40.0 parts Cyclohexanone 51.0 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 8.0 parts Dispersing aid ("Solsper's 20000" manufactured by Avicia) 1.0 part Acrylic resin solution 1 40.0 parts Cyclohexanone 51.0 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 8.0 parts Dispersing aid ("BYK111" manufactured by Big Chemie) 1.0 part Acrylic resin solution 2 40.0 parts Cyclohexanone 51.0 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 pigments 8.0 parts Dispersing aid ("BYK111" manufactured by Big Chemie) 1.0 parts Acrylic resin solution 2 40.0 parts Cyclohexanone 51.0 parts

(Production of red coloring composition)
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 50.0 parts Acrylic resin solution 3 10.0 parts Trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 1.8 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 10.0 parts

(Production of green coloring composition)
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 30.0 parts Yellow pigment dispersion 20.0 parts Acrylic resin solution 3 10.0 parts Trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 1.8 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 10.0 parts

(Production of blue coloring composition)
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 10.0 parts Trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 1.8 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 10.0 parts [Example 1]

The red coloring composition obtained above was applied with a spin coater so that the dry film thickness was 2.0 μm, 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 red pixels on the substrate. Next, a green pixel was similarly formed using the green coloring composition, and a blue pixel was further formed using the blue coloring composition, thereby obtaining a color filter layer.
When the thickness direction retardation Rth was measured for the substrate on which the color filter layer was formed, the red pixel portion had a wavelength of 630 nm, the green pixel portion had a wavelength of -18 nm, and the blue pixel portion had a wavelength of 450 nm. It was 2 nm in light (here, Rth is obtained by multiplying the product of the value obtained by subtracting the refractive index in the thickness direction from the average in-plane refractive index of the pixel at the wavelength and the thickness (μm) of the pixel by 1000) Represents a numeric value).

A liquid crystal compound obtained by stirring and mixing a mixture having the following composition uniformly and filtering through a 0.6 μm filter is applied onto the color filter layer of the substrate to a dry film thickness of 0.7 μm using a spin coater. Then, it was heated and dried at 90 ° C. for 2 minutes on a hot plate to obtain a liquid crystal alignment substrate.
Vertical alignment polymerizable liquid crystal 19.0 parts (Dainippon Ink Chemical Co., Ltd. "UCL-018")
Photopolymerization initiator 1.0 part ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 3.0 parts (Bikchemy "BYK111" 2% cyclohexanone solution)
77.0 parts of cyclohexanone

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 dose of ultraviolet rays, 500 mJ / cm ² in the red pixel region, 5 mJ / cm ² in the green pixel region and a blue pixel region was 20 mJ / cm ^2.

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 sum of the thickness direction retardation Rth of the color filter layer and the retardation film of the color filter substrate was measured, the red pixel portion was −81 nm in the light of wavelength 630 nm, the green pixel portion was −80 nm in the light of wavelength 550 nm, blue The pixel portion was −81 nm in light having a wavelength of 450 nm. The results are shown in Table 1.

［実施例２］

[Example 2]

After forming a color filter layer on a glass substrate in the same manner as in Example 1, the liquid crystal compound obtained by stirring and mixing a mixture having the following composition uniformly and filtering through a 0.6 μm filter was used as the color filter of the substrate. On the layer, it apply | coated so that the dry film thickness might be set to 3.3 micrometers with a spin coater, and it heat-dried at 90 degreeC for 2 minute (s) with the hotplate, and obtained the liquid crystal aligning substrate.
Horizontally-aligned polymerizable liquid crystal 18.3 parts (“Palocolor LC 242” manufactured by BASF Japan Ltd.)
1.5 parts of chiral agent ("Palocolor LC 756" manufactured by BASF Japan Ltd.)
Photopolymerization initiator 0.2 part ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 3.0 parts (Bikchemy "BYK111" 2% cyclohexanone solution)
77.0 parts of cyclohexanone

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 dose of ultraviolet rays, 50 mJ / cm ² in the red pixel region, 500 mJ / cm ² in the green pixel region and a blue pixel region was 200 mJ / cm ^2.

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 sum of the thickness direction retardation Rth of the color filter layer and the retardation film of the color filter substrate was measured, the red pixel portion was 152 nm for light with a wavelength of 630 nm, the green pixel portion was 150 nm for light with a wavelength of 550 nm, and the blue pixel portion Was 152 nm in light having a wavelength of 450 nm. The results are shown in Table 2.

［実施例３］

[Example 3]

The red coloring composition obtained above was applied with a spin coater so that the dry film thickness was 1.0 μm, 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 red pixels on the substrate. Next, a green pixel was similarly formed using the green coloring composition, and a blue pixel was further formed using the blue coloring composition, thereby obtaining a color filter layer.
When the in-plane phase difference Re was measured for the substrate on which the color filter layer was formed, no phase difference was confirmed in any color pixel.

  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.

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 part ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 6.0 parts ("BYK111" 2% cyclohexanone solution manufactured by Big Chemie)
Cyclohexanone 154.0 parts

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 dose of ultraviolet rays, 500 mJ / cm ² in the red pixel region, 200 mJ / cm ² in the green pixel region and a blue pixel region was 5 mJ / cm ^2.

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 sum of the thickness direction retardation Rth of the color filter layer and the retardation film of the color filter substrate was measured, the red pixel portion was 152 nm for light with a wavelength of 630 nm, the green pixel portion was 150 nm for light with a wavelength of 550 nm, and the blue pixel portion Was 152 nm in light having a wavelength of 450 nm. The results are shown in Table 3.

The schematic of the phase difference substrate (when it is set as a color filter substrate) of this invention is shown.

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 (11)

In a retardation substrate including at least a substrate and a liquid crystal fixing layer provided on the substrate,
The liquid crystal immobilization layer has optical anisotropy, and the liquid crystal immobilization layer is provided so that the birefringence is different for each of a plurality of regions due to different degrees of orientation. A characteristic retardation substrate. In a retardation substrate including at least a substrate and a liquid crystal fixing layer provided on the substrate,
The liquid crystal immobilization layer has optical anisotropy, and the liquid crystal immobilization layer is continuously provided so that the birefringence is different for each of a plurality of regions due to different degrees of orientation. A retardation substrate, which is a film. A retardation substrate comprising at least a substrate and a liquid crystal immobilization layer, which is produced from a production method including the following steps.
(A) A thin film in which the liquid crystal compound is aligned in a predetermined direction is formed on a substrate by applying a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or crosslinked by light. The process of
(B) a step of irradiating the substrate with light so as to have a different dose for each region;
(C) heating the liquid crystal compound to an isotropic phase transition temperature or higher;
(D) A step of curing an uncured liquid crystal compound to form a liquid crystal immobilization layer. A retardation substrate comprising at least a substrate and an immobilization layer, which is produced from a production method including the following steps.
(A) A thin film in which the liquid crystal compound is aligned in a predetermined direction is formed on a substrate by applying a solution containing a compound that exhibits thermotropic liquid crystallinity and can be polymerized and / or cross-linked by light. The process of
(B) a step of irradiating the substrate with light so as to have a different dose for each region;
(C) heating the liquid crystal compound to an isotropic phase transition temperature or higher;
(D) A step of exposing the entire surface of the substrate while maintaining the temperature at which the liquid crystal compound is kept in an isotropic phase to form a liquid crystal fixed layer.   3. The retardation substrate according to claim 1, wherein the liquid crystal fixing layer is formed by polymerizing and / or crosslinking a compound containing a thermotropic liquid crystal. 4.   6. The retardation substrate according to claim 1, wherein any one of glass, plastic, and a film substrate is used as the substrate.   2. The liquid crystal fixing layer according to claim 1, wherein the phase difference has a predetermined value for each color so as to optically compensate the incident light transmitted through the color filter for each color. The phase difference substrate for a color filter according to any one of 6.   The retardation substrate according to claim 1, wherein the liquid crystal fixing layer has a uniform thickness.   The retardation substrate according to claim 1, wherein a TFT is provided between the liquid crystal fixing layer and the substrate.   The retardation substrate according to claim 1, further comprising a TFT provided on the liquid crystal immobilization layer.   A liquid crystal display device using the retardation substrate according to claim 1.

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