JP4920584B2 - Color filter and liquid crystal display device using the same - Google Patents

Description

  The present invention relates to a color filter for a liquid crystal display device and a liquid crystal display device, and in particular, a liquid crystal display having excellent display contrast, no TFT malfunction, no display unevenness, and high color purity and high transmittance. The present invention relates to a device color filter and a liquid crystal display device.

  A color filter used for a color liquid crystal display or the like has a color pixel (R, G, B) formed on a transparent substrate, and a gap between each color pixel of R (red), G (green), and B (blue). A black matrix is formed for the purpose of improving display contrast. In particular, a black matrix used in an active matrix driving type liquid crystal display element using a thin film transistor (TFT) has a high light-shielding property in addition to the above purpose, in order to prevent deterioration in image quality due to current leakage due to light from the thin film transistor. Sex is required.

    As a known example of a method for forming a black matrix using a metal film such as chromium as a light shielding layer, a metal thin film is prepared by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then a black matrix is used. Includes methods including exposing and developing a photoresist layer through a photomask having a pattern, etching the exposed metal thin film, and finally stripping the resist layer on the metal thin film (eg, “color TFT "Liquid Crystal Display" pp. 218-220 (Kyoritsu Shuppan Co., Ltd., published April 10, 1997)).

  Since this method uses a metal thin film, a high light shielding effect can be obtained even if the film thickness is thin. On the other hand, there is a problem that a vacuum film forming process such as a vapor deposition method or a sputtering method or an etching process is required, and the cost increases and the burden on the environment cannot be ignored. Further, this method has a problem that the reflectance increases because of the metal film, which causes a malfunction of the TFT and a decrease in contrast in the bright room. For these problems, a means of using a low-reflective chromium film (such as two layers of metal chromium and chromium oxide) can be taken, but it cannot be denied that this means increases the cost.

  In addition, as another known example of a method for forming a black matrix, a method using a photosensitive resin composition containing a light-shielding pigment (for example, carbon black) is also known. In this so-called self-alignment black matrix forming method, R, G, and B pixels are formed on a transparent substrate, and then a carbon black-containing photosensitive resin composition is applied to the pixels, and the R of the transparent substrate is applied. And a step of exposing the entire surface from the non-G, B pixel forming surface side (for example, JP-A-62-9301).

  In this method, although the manufacturing cost is lower than the method by etching the metal film, the film thickness necessary for obtaining sufficient light shielding property (for example, OD = 4.0) is 1.1 to 1.4 μm. A degree is required. As a result of this increase in film thickness, there is an overlap (step) between the black matrix and each of the R, G, and B pixels, the flatness of the color filter is degraded, and the cell gap of the liquid crystal display element is uneven. , Leading to display defects such as color unevenness.

Therefore, in order to obtain a thin film having a high OD, a technique for producing a light-shielding film for producing a black matrix using a photosensitive resin composition containing metal particles has been proposed (Japanese Patent Application Laid-Open No. 2004-240039). ).
Furthermore, in order to make the color of the black matrix close to black, a black matrix having a light-shielding film containing metal particles and pigment fine particles has been proposed (Japanese Patent Laid-Open No. 2004-317897).

However, when the content of the metal particles in the black matrix is large, the reflectance increases due to the metallic luster, so that there is a problem that the bright room contrast is lowered when a color filter is produced using the black matrix. Further, when the content of the black pigment fine particles in the black matrix is large, it is difficult to make the black matrix thin, and the thickness of the black matrix becomes thick. As a result, there is an overlap (step) between the black matrix and R, G, B (red, green, blue) pixels, the flatness of the color filter is deteriorated, the cell gap unevenness of the liquid crystal display element occurs, and the color It leads to display defects such as unevenness.
"Color TFT LCD", pages 218-220 (Kyoritsu Publishing Co., Ltd., published April 10, 1997) JP-A-62-9301 JP 2004-240039 A JP 2004-317897 A

  The present invention has been made in view of the above circumstances. The present invention provides a color filter for a liquid crystal display device and a liquid crystal display device having excellent display contrast in a bright room, no TFT malfunction, no display unevenness, and having both high color purity and high transmittance. To do.

The above object of the present invention is achieved by providing a color filter for a liquid crystal display device and a liquid crystal display device having the following constitution.
(1) A color filter for a liquid crystal display device comprising a transparent substrate and a black matrix provided on the transparent substrate,
Including G (green) colored pixels in a region to be separated of the black matrix;
A part of the colored layer of the G (green) colored pixel is laminated on a part of the black matrix;
The black matrix is selected from a pigment , metal particles selected from gold, silver, copper, platinum, palladium, and tin , and metal alloy particles containing these metals , and gold, silver, copper, platinum, and palladium. Containing at least one selected from metal compound particles containing a metal;
The ratio (B / A) of pigment content B to content A of the metal particles (including metal alloy particles) and metal compound particles in the black matrix is in the range of 0.2 to 10; A film thickness ratio (TG / BM) between a film thickness TG of a (green) colored pixel and a film thickness BM of a black matrix is in a range of 1.2 to 10, wherein the color filter for a liquid crystal display device .
(2) Further including an R (red) colored pixel and a B (blue) colored pixel in a region to be separated from the black matrix;
The film thickness ratio TR / BM of the R (red) colored pixel and the BM is in the range of 1.2 to 10; and the film thickness TB of the B (blue) colored pixel The color filter for a liquid crystal display device according to (1), wherein a film thickness ratio (TB / BM) between the BM and the BM is in a range of 1.2 to 10.
(3) The height of the protruding portion formed by laminating a part of the colored layer of the colored pixel on a part of the black matrix is 0.4 μm or less with respect to the colored pixel. The color filter for a liquid crystal display device according to the above (1) or (2).
(4) The liquid crystal display device according to any one of (1) to (3), wherein a transmission density of the black matrix is 3.5 or more and a film thickness is 1.3 μm or less. Color filter.
(5) The chromaticity point on the CIE chromaticity diagram by the G (green) C light source described above is in the chromaticity range of G (x ≦ 0.32, y ≧ 0.56). The color filter for liquid crystal display device according to any one of (1) to (4).
(6) The chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors R (red), G (green), and B (blue) described above is R (x ≧ 0.62, y ≦ 0). .35), G (x ≦ 0.32, y ≧ 0.56), and B (x ≦ 0.17, y ≦ 0.14). The color filter for a liquid crystal display device according to any one of (5).
(7) The color filter for a liquid crystal display device according to any one of (1) to (6), wherein the pigment contains at least one selected from carbon black and graphite.
(8) The metal particles (including metal alloy particles) or metal compound particles contained in the black matrix are metal particles, wherein the metal particles are any one of (1) to (7). Color filter for liquid crystal display devices.
(9) The metal particles (including metal alloy particles) or metal compound particles contained in the black matrix include at least one selected from Ag fine particles , AgSn alloy fine particles , silver sulfide fine particles, and tin fine particles. The color filter for a liquid crystal display device according to any one of (1) to (7), wherein the color filter is a liquid crystal display device color filter.
(10) The black matrix comprising a photosensitive resin composition containing the pigment and at least one selected from the metal particles (including metal alloy particles) and metal compound particles (1) The color filter for liquid crystal display devices of any one of (1)-(9).
(11) The black matrix includes a photosensitive transfer material containing the pigment and at least one selected from the metal particles (including metal alloy particles) and metal compound particles. The color filter for liquid crystal display devices of any one of-(10).
(12) A liquid crystal display device comprising the color filter for a liquid crystal display device according to any one of (1) to (11).

  With the color filter for liquid crystal display device and the liquid crystal display device of the patented invention, display contrast in a bright room is high, TFT does not malfunction, there is no display unevenness, and both high color purity and high transmittance are compatible. Can do.

It is explanatory drawing which shows one Embodiment of the thickness of the coloring pixel in a comparative example, and the height of a projection part. It is explanatory drawing which shows other embodiment of the thickness of the coloring pixel in this invention, and the height of a projection part.

The color filter for a liquid crystal display device of the present invention has a black matrix on a transparent substrate. The black matrix has at least G (green) colored pixels in a region to be separated. A part of the colored layer of the G (green) colored pixel is laminated on a part of the black matrix. The black matrix contains a pigment and metal particles and / or metal compound particles. The ratio (mass ratio) (B / A) of the content A of the metal particles and / or metal compound particles and the content B of the pigment (B / A) is from 0.2 to 10. The ratio (film thickness ratio) (TG / BM) of the film thickness TG of the G (green) colored pixel to the film thickness BM of the black matrix is 1.2 or more and 10 or less.
Hereinafter, the main components of the color filter for a liquid crystal display device of the present invention will be described in detail. However, the present invention is not limited to these explanation items.

In the present invention, the black matrix contains at least a pigment and at least one of metal particles (including metal alloy particles) and metal compound particles. These are contained in the black matrix at least in a dispersed state in the polymer compound.
Metal particles used in the present invention (hereinafter, appropriately referred to as "metal particles", including a metal alloy particles.) Are gold, silver, copper, platinum, metal particles selected from palladium, and tin, and their It is a metal alloy particle containing a metal . Among these, gold, silver, and copper are particularly preferable, and silver is particularly preferable. The silver contained in the metal particles of the present invention is most preferably colloidal silver. In the production of metal particles, two or more of the above metals may be used in combination. Further, for the production of metal particles, it is also possible to use an alloy composed of two or more of the above metals.

Commercially available metal particles can be used. The metal particles can also be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
Examples of a method for preparing silver fine particles (colloidal silver) include a method of reducing a soluble silver salt with hydroquinone in an aqueous gelatin solution disclosed in US Pat. No. 2,688,601, German Patent 1, Silver ions as in the method of reducing a sparingly soluble silver salt described in US Pat. No. 096,193 with hydrazine, the method of reducing to silver with tannic acid described in US Pat. No. 2,921,914 In a solution, a method of forming silver particles by electroless plating described in JP-A-5-134358, a bulk metal is evaporated in an inert gas such as helium, and a solvent is used. Conventionally known methods such as a method such as vapor evaporation in a cold trap are included. An example of a method for preparing silver fine particles (colloidal silver) is a method for preparing yellow colloidal silver by the dextrin reduction method of Carey Le described in Colloidal Elements by Weiser published in Wiley & Sons, New York, 1933. Is also included.

The “metal compound” referred to in the present invention is a compound of the metal and an element other than the metal.
Examples of compounds of metals and other elements include metal oxides, sulfides, sulfates, carbonates and the like. Of these, sulfide is particularly preferred from the viewpoint of color tone and ease of fine particle formation. Examples of these metal compounds include copper (II) oxide, iron sulfide, silver sulfide, copper (II) sulfide, titanium black and the like. Among these, silver sulfide is particularly preferable from the viewpoints of color tone, ease of fine particle formation, and stability.

Examples of the metal compound particles referred to in the present invention include the following.
(1) Fine particles composed of the above metal compound (2) Fine particles composed of two or more kinds of metal compound particles combined into one particle (3) Fine particles composed of metal particles and metal compound particles Two or more kinds of metal compound particles Specific examples of the composite fine particles include composite fine particles of silver and silver sulfide, composite fine particles of copper sulfide and silver sulfide, and composite fine particles of silver and copper (II) oxide.

Specific examples of the fine particles composed of metal particles and metal compound particles include composite fine particles of silver and silver sulfide, composite fine particles of copper sulfide and silver sulfide, and composite fine particles of silver and copper (II) oxide.
There is no particular limitation on the shape of the composite fine particles. Examples of the shape include a shape having a different composition between the inside and the surface of the particle, a shape in which two types of particles are combined, and the like.

There is no restriction | limiting in particular in the particle size of the metal particle and / or metal compound particle which are used by this invention. The average particle size is preferably in the range of 10 to 3000 nm, more preferably the average particle size is in the range of 30 to 2000 nm, and further preferably in the range of about 60 to 200 nm. However, in the case of the metal compound particles (not composite fine particles) of (1) above, those having an average particle diameter of less than 60 nm may have a slightly inferior color tone. A particle size exceeding 3000 nm may not be preferable from the viewpoint of dispersibility.
There are no particular restrictions on the particle size distribution of the metal particles and / or metal compound particles.

The metal particles and / or metal compound particles used in the present invention must be colored in order to obtain a necessary optical density. Here, “colored” means optical absorption in the wavelength region of 400 to 700 nm. Examples of the colored metal compound include silver sulfide, copper sulfide, iron sulfide, palladium sulfide, silver oxide, titanium black and the like.
There is no restriction | limiting in particular in the shape of the metal particle and / or metal compound particle | grains of this invention. Examples of the particle shape that can be used include a sphere, an indeterminate shape, a plate shape, a cube, a regular octahedron, and a column shape.
If necessary, two or more kinds of metal particles and / or metal compound particles having different compositions, shapes, particle sizes, and optical absorption wavelength regions can be mixed and used.
In addition, about the manufacturing method of a metal particle, it describes, for example in "The latest trend II in the technique and application of an ultrafine particle II (Sumi-Petechno Research Co., Ltd. issue, 2002).

Pigment In the present invention, black pigment fine particles are particularly preferably used as the pigment. Examples thereof include Pigment Black 7 (carbon black CI No. 77266, for example, trade name: Mitsubishi Carbon Black MA100 (manufactured by Mitsubishi Chemical Corporation), trade name: Mitsubishi Carbon Black # 5 (Mitsubishi Chemical Corporation) Product name: Black Pearls 430 (manufactured by Cabot Co. (Cabot)), graphite, etc. Among these, carbon black and graphite are particularly preferable.

  The average particle size of the metal particles and pigment fine particles in the present invention is obtained by measuring 50 particle sizes by observation with a transmission electron microscope (TEM) and calculating the average value.

  The ratio (mass ratio B / A) of the amount A of the metal particles and / or metal compound particles contained in the black matrix constituting the color filter of the present invention to the amount B of the pigment is in the range of 0.2 to 10, Preferably it exists in the range of 0.3-6.0, More preferably, it exists in the range of 0.8-5.0. When the mass ratio B / A is less than 0.2, the addition amount of metal particles and / or metal compound particles in the black matrix is large, so that the reflectivity of the black matrix is increased, and thus the malfunction of the TFT is likely to occur. . On the other hand, when the mass ratio B / A exceeds 10, the transmission optical density of the black matrix is lowered and the predetermined transmission optical density is maintained because there are few metal particles and / or metal compound particles in the black matrix. It is necessary to increase the thickness of the black matrix. As a result, an overlap (step) occurs between the black matrix and each of the R, G, and B pixels, so that the flatness of the color filter is deteriorated and the cell gap of the liquid crystal display element is uneven. This unevenness tends to lead to display defects such as color unevenness in the liquid crystal display device of the present invention.

  In addition, the film thickness ratio (TG / BM) of the thickness (TG) of the G (green) colored pixel having the highest visibility among the RGB pixels constituting the color filter of the present invention and the thickness (BM) of the black matrix. ) Is in the range of 1.2 to 10, preferably in the range of 1.4 to 5.0, more preferably in the range of 2.0 to 4.0. Further, the film thickness ratios TR / BM, TG / BM, and TB / BM of the film thicknesses TR, TG, TB of the colored pixels of R (red), G (green), and B (blue) and the film thickness BM of the black matrix Are preferably in the range of 1.2 to 10, more preferably the ratio of these film thicknesses is in the range of 1.4 to 5.0. More preferably, it is in the range of 0 to 4.0.

  Here, the film thickness of the colored pixel is as follows. That is, in FIG. 1, the thickness of the colored pixel is the thickness of the flat portion of the colored pixel 10 and is the thickness indicated by Ha. (BM> Ha in FIG. 1) Also, in FIG. 2, the thickness of the colored pixel is the thickness of the flat portion of the colored pixel 12, which is the thickness indicated by Hc. (Hc> BM in FIG. 2)

  In the present invention, the height of the protruding portion formed by laminating a part of the colored layer of the colored pixel (G) on the part of the black matrix is 0 to 0.4 μm. Preferably, it is in the range of 0 to 0.3 μm, more preferably in the range of 0 to 0.2 μm. Here, the protrusion height of the protrusion on the black matrix is as follows. That is, in FIG. 1, the protrusion height refers to the height (thickness) of the protruding portion from the thickness of the flat portion of the colored pixel 10 on the black matrix (BM), and refers to the film thickness Hb of the protruding portion. In FIG. 2, the protrusion height refers to the height (thickness) of the protruding portion from the thickness of the flat portion of the colored pixel 12, and refers to the film thickness Hd of the protruding portion. If the height (thickness) of the protruding portion of the colored pixel on the black matrix is larger than 0.4 μm, color unevenness due to the liquid crystal alignment due to the thickness difference of the pixel through which light passes may occur, which is not preferable.

It is preferable that the transmission density of the black matrix is in the range of 3.5 to 10.0 and the film thickness is in the range of 0.1 to 1.3 μm. More preferably, the transmission density is 3.8 or more and the film thickness is 1.1 μm or less. More preferably, the transmission density is 4.0 or more and the film thickness is 1.0 μm or less. If the transmission density of the black matrix is high and the film thickness is thin enough to keep the light shielded, the black matrix and the R, G, and B pixels do not easily overlap (steps). Improved. Therefore, unevenness due to the cell gap of the liquid crystal display element hardly occurs, and display defects such as color unevenness do not occur.
Examples of means for controlling the transmission density and film thickness of the black matrix within the above range include adjusting the mass ratio of the pigment and the metal particles and / or metal compound particles in the black matrix to a predetermined range. Etc. are included.

Black Matrix The black matrix of the present invention is preferably formed from a resin composition containing a pigment, metal particles and / or metal compound particles, and further containing a polymer serving as a binder, a dispersion stabilizer, a surfactant and the like. In particular, the black matrix is preferably formed of a photosensitive resin composition having photosensitivity and containing metal particles (hereinafter also referred to as “a composition for producing a black matrix”). Examples of the photosensitive resin composition for imparting such photosensitivity include those described in paragraphs [0016] to [0022] and [0029] of JP-A No. 10-160926.

  When the metal particles are used in the form of an aqueous dispersion like the silver colloid, the black matrix preparation composition is preferably an aqueous medium composition. Examples of such a composition for preparing an aqueous black matrix include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and suitable examples of the commercially available composition include: SPP-M20 (trade name, manufactured by Toyo Gosei Co., Ltd.) and the like are included.

The black matrix preparation composition may be prepared by adding a photopolymerizable compound, a photopolymerization initiator, an inhibitor, and the like.
Preferable examples of the photopolymerizable compound used in the composition for producing a black matrix include a monomer or oligomer having an ethylenically unsaturated double bond and capable of addition polymerization by irradiation with light. Examples of such a monomer or oligomer include a compound having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
Specific examples of the photopolymerizable compound include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Sundiol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; and trimethylolpropane, glycerin, etc. Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol and then (meth) acrylated are included.

  Specific examples of the photopolymerizable compound further include urethane acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; Polyester acrylates described in Japanese Patent No. 64183, Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates such as epoxy acrylate which is a reaction product of epoxy resin and (meth) acrylic acid Mention may be made of straw and methacrylate. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are also included.

  The above monomers or oligomers may be used singly or in combination of two or more. The content of the photopolymerizable compound relative to the total solid content of the black matrix preparation composition is generally 5 to 50% by mass, and particularly preferably 10 to 40% by mass.

  Examples of the photopolymerization initiator used in the composition for producing a black matrix of the present invention include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660 and US Pat. No. 2,448,828. Acyloin ether compounds, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758 A combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound and a trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, and US Pat. No. 4,239,850. Trihalomethyl-s described in the specification Triazine compounds, etc. U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable. The content of the photopolymerization initiator based on the total solid content of the black matrix preparation composition is generally 0.5 to 20% by mass, and particularly preferably 1 to 15% by mass.

  The composition for preparing a black matrix in the present invention can further contain an inhibitor (thermal polymerization inhibitor). Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

The black matrix preparation composition of the present invention may further contain various additives such as a plasticizer, a surfactant, an adhesion promoter, an ultraviolet absorber, a solvent and the like, if necessary.
The composition for producing a black matrix in the present invention is prepared as a coating solution in which the above-described solid components are dissolved or dispersed in a solvent, and this is applied to the surface of a substrate, a temporary support or the like and dried to form a colored resin layer. Used to form.

  Examples of the organic solvent used in the preparation of the composition for producing a black matrix include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, ethyl lactate, methyl lactate, caprolactam and the like.

  The film thickness of the resin layer for black matrix (hereinafter also referred to as “light-shielding layer”) was determined by using the composition of the spacer portion, the cell gap, and the black matrix preparation composition finally formed on the color filter. It is determined in consideration of the reduction rate of the film thickness in the black matrix forming process.

  The composition for black matrix preparation in the present invention can be applied to a substrate or the surface of a temporary support described later by a known method and dried to form a photosensitive sheet (light-shielding layer).

  Examples of the means for applying the black matrix preparation composition include a slit coater, a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, a wire bar coater, and an extruder. The formed coating layer is then dried to obtain a photosensitive resin layer or a photosensitive transfer sheet.

Photosensitive transfer material In the present invention, a photosensitive transfer material is prepared using the above-described pigment for forming a black matrix having photosensitivity and a composition containing metal particles and / or metal compound particles, and the photosensitive transfer material. Can be used to produce a black matrix. The photosensitive transfer material is provided with a photosensitive light-shielding layer comprising a black matrix-forming composition containing at least the above-mentioned photosensitivity and containing pigments and metal particles and / or metal compound particles on a temporary support. It is. The film thickness of the photosensitive light-shielding layer is preferably in the range of about 0.3 to 3.0 μm, and more preferably in the range of about 0.5 to 2.0 μm.

  The photosensitive transfer material is basically the same as a known photosensitive transfer material except that the photosensitive pigment and the metal particle and / or metal compound particle-containing composition are used as the photosensitive resin material. Can have a configuration. An example of the structure of a known photosensitive transfer material is described in JP-A-5-173320. The most basic structure of such a photosensitive transfer material is a temporary support sheet made of a flexible plastic film or the like, and a thin layer made of a composition for producing a black matrix formed on the temporary support sheet. including. Between the temporary support sheet and the light shielding layer, an undercoat layer or an intermediate layer such as a layer that facilitates peeling between them and a cushioning layer for the light shielding layer can be optionally provided. Examples of a preferable configuration include a configuration in which an alkali-soluble thermoplastic resin layer, an intermediate layer, and a light shielding layer are formed on a temporary support sheet. A protective film may optionally be further laminated on the light shielding layer.

  As the temporary support, intermediate layer, and thermoplastic resin layer in the present invention, the same temporary support, intermediate layer, and thermoplastic as described in paragraphs “0034” to [0040] of JP-A-2004-347801. A resin layer can be used.

  In the process of producing the photosensitive transfer material of the present invention, a solution of the black matrix-producing composition containing the photosensitive and metal particles of the present invention on a temporary support, for example, a slit coater, spinner, A step of applying and drying using a coating means such as a winder, a roller coater, a curtain coater, a knife coater, a wire bar coater, and an extruder may be included. In the case of providing the alkali-soluble thermoplastic resin layer, the alkali-soluble thermoplastic resin layer can also be produced in the same process.

  Since the photosensitive transfer material of the present invention is provided with the photosensitive light-shielding layer comprising the pigment and the metal particle and / or metal compound particle-containing composition as described above, the transfer material is used to form a thin film and have an optical density. A black matrix can be produced by providing a high light shielding layer.

Production of Black Matrix The black matrix of the present invention comprises the above-described (photosensitive) pigment particles and a light-shielding layer produced using a metal particle and / or metal compound particle-containing composition or a photosensitive transfer material having this composition. It is formed. The film thickness of the black matrix is generally about 0.1 to 1.3 μm. Since the black matrix of the present invention is obtained by uniformly dispersing pigment particles and metal particles and / or metal compound particles, even a thin film having a film thickness within the above range exhibits a sufficient optical density (shielding performance). Can do.

Examples of a method for producing a black matrix using a photosensitive pigment particle and a composition containing metal particles and / or metal compound particles include a light-transmitting substrate, photosensitive metal particles and / or The layer formed by applying the metal compound particle-containing composition (light-shielding layer) includes a method of forming a black matrix by exposing through a photomask for black matrix by a conventional method and then developing the layer. . As a method for applying the metal particle and / or metal compound particle-containing composition, the application method used for producing the photosensitive transfer material can be similarly used.
In addition, when the pigment particle and the metal particle and / or metal compound particle-containing composition are not photosensitive, the pigment particle and the metal particle and / or metal compound particle-containing composition are applied to the light-transmitting substrate. A black matrix can be formed by forming a layer from a developable photosensitive resin composition on the exposed layer, exposing through a photomask for black matrix by a conventional method, then developing and etching. .

  The method for producing the black matrix using the photosensitive transfer material is the method of laminating the photosensitive transfer material on a light-transmitting substrate so that the photosensitive light-shielding layer of the photosensitive transfer material is in contact with the laminate. Next, the temporary support is peeled from the laminate of the photosensitive transfer material and the light-transmitting substrate, and then the photosensitive light-shielding layer is exposed through a black matrix photomask, followed by development to form a black matrix. Etc. can be used. Thus, the manufacturing method of the black matrix of this invention does not require a complicated process, and is simple and low-cost.

Next, the composition for colored pixels used for the color filter of the present invention will be described.
Examples of the composition that can be used as the coloring composition for the color filter of the present invention include the compositions described in paragraph numbers [0046] to [0056] of JP-A No. 2004-347831.

Among the above pigments, the R (red) pixel of the color filter for a liquid crystal display device of the present invention is at least C.I. as a pigment from the viewpoint of obtaining high color purity and flatness. I. Pigment Red 254 (C.I.PR-254) is preferably contained.
The G (green) pixel of the color filter of the present invention has at least C.I. as a pigment from the viewpoint of obtaining high color purity and flatness. I. Pigment Green 36 (C.I.PG-36) and C.I. I. Pigment Yellow 138 (C.I.PY-138), C.I. I. Pigment Yellow 139 (C.I.PY-139), C.I. I. It is preferable to contain any one of CI Pigment Yellow 150 (CI PY-150).
Further, from the viewpoint of obtaining high color purity and flatness, the B (blue) pixel of the color filter of the present invention has at least C.I. I. Pigment Blue 15: 6 (C.I.PB-15: 6) is preferably contained.

The above pigment system has a transmission region on the long wave side and can achieve high color purity. Moreover, the dispersibility and stability of a pigment are favorable, and it has the physical property suitable for the color filter use for liquid crystal display devices of this invention.
In the pigment composition of the present invention, the content of the colorant (pigment) is preferably in the range of 0.1 to 70% by mass with respect to the total solid content mass of the composition, 0.5 to 60 More preferably in the range of mass%, particularly preferably in the range of 1.0 to 50 mass%.

By selecting the pigment system as described above, the chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors R (red), G (green), and B (blue) is G (x ≦ 0 .32, y ≧ 0.56), more preferably R (x ≧ 0.62, y ≦ 0.35), G (x ≦ 0.32, y ≧ 0.56), B (x ≦ 0) .17, y ≦ 0.14), a suitable color filter for a liquid crystal display device can be obtained. Thus, the HDTV standard, which is the main chromaticity standard for TV applications, that is, R (x = 0.64, y = 0.33), G (x = 0. 3, y = 0.6) and B (x = 0.15, y = 0.06) can be achieved to achieve high color purity.
Examples of the method of measuring the chromaticity point on the CIE chromaticity diagram with the C light source of the color filter include a method of measuring each pixel formed on the transparent substrate using a microspectrophotometer, or a 3 cm square A method of manufacturing a pixel having a size and measuring with a normal ultraviolet-visible spectrophotometer is included.

  In the present invention, a suitable pigment is desirably used in the state of a dispersion. Examples of such a dispersion include dispersions described in paragraph numbers [0058] to [0059] of JP-A No. 2004-347831.

Production of Color Filter The color filter of the present invention has at least R (red), G (green), and B (blue) colored pixel groups on a light-transmitting substrate, and each of the pixel groups constituting the pixel group. The pixels are separated from each other by a black matrix, and the black matrix is produced using the above-described coloring composition for forming a black matrix or a photosensitive transfer material of the present invention. These at least three types of pixel groups of red, green, and blue are preferably arranged in a mosaic type, a stripe type, or a triangle type.
Examples of the light-transmitting substrate include a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a known glass plate such as a quartz glass plate, or a plastic film.

  The method for producing a color filter may include a step of forming a black matrix as described above after forming two or more pixel groups on a light-transmitting substrate by a conventional method. Alternatively, a process of forming a black matrix first and then forming two or more pixel groups may be included. Since the color filter of the present invention includes the black matrix as described above, it has high display contrast and excellent flatness.

Below, the manufacturing method of the color filter of this invention is demonstrated in detail. The color filter of the present invention can be manufactured for each of R, G, and B pixels. Examples of the manufacturing method may include sequentially performing the following steps.
(1) A photosensitive colored resin layer is provided on a substrate by bonding a photosensitive sheet made of a color composition for producing a color filter containing a photopolymerizable compound, a photopolymerization initiator, a binder, a coloring component (pigment), and the like. Process;
(2) A step of exposing the photosensitive colored resin layer in a pattern;
(3) a step of developing the exposed photosensitive colored resin layer to obtain a patterned colored cured film layer composed of an exposed portion of the photosensitive colored resin layer; and (4) the patterned colored cured film layer. The process of baking and further curing by heating.
The steps (1) to (4) can be performed in the same manner as the method described in paragraph numbers [0062] to [0065] of JP-A-2004-347831.

Liquid Crystal Display Device One embodiment of the liquid crystal display device of the present invention includes a color filter, a liquid crystal layer, and liquid crystal driving means (simple matrix driving method or active matrix driving method) between a pair of substrates, at least one of which is light transmissive. ) At least. The color filter has a pixel group of at least three colors. The pixels constituting the pixel group are separated from each other by the black matrix of the present invention. Since the color filter of the present invention has high flatness, the liquid crystal display device including this color filter does not cause cell gap unevenness between the color filter and the substrate. Therefore, display defects such as color unevenness do not occur.
In another aspect of the liquid crystal display device of the present invention, a color filter, a liquid crystal layer, and liquid crystal driving means are provided between at least one pair of light-transmitting substrates. The liquid crystal driving means includes active elements (for example, TFTs), and includes a color filter in which the three-color pixel group of the present invention and a black matrix are formed between the active elements.

  A preferred example of the liquid crystal display device of the present invention using the color filter of the present invention has a three-wavelength light source, and has a backlight and the three primary colors of R (red), G (green), and B (blue). In combination with a pixel. Here, in the liquid crystal display device of the present invention, the chromaticity point on the CIE chromaticity diagram by the C light sources of the three primary colors R (red), G (green), and B (blue color) is R (x ≧ 0). .62, y ≦ 0.35), G (x ≦ 0.32, y ≧ 0.56), and B (x ≦ 0.17, y ≦ 0.14).

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the examples, “parts”, “%” and “molecular weight” represent “parts by mass”, “mass%” and “mass average molecular weight” unless otherwise specified.

Preparation of Carbon Black Dispersion A carbon black dispersion having the following formulation was prepared using a zirconia bead having a diameter of 0.65 mm using a motor mill (trade name: M50, manufactured by Eiger Corporation).
-Normal propanol 69 parts-Methacrylic acid / allyl methacrylate copolymer (copolymerization ratio = 20:80)-10 parts-Dispersant (trade name: Solsperse 20000, manufactured by Avicia) 1 part-Carbon black (trade name: Carbon black MA100, manufactured by Mitsubishi Chemical Corporation) 20 parts

Preparation of silver particles 3488 g of distilled water was added to 112 g of gelatin, and the resulting mixture was heated to about 47 ° C. to dissolve the gelatin. To this was added 4.0 g calcium acetate and 2.0 g potassium borohydride. Immediately thereafter, 6.0 g of silver nitrate dissolved in 1.0 L of distilled water was added with rapid stirring. Further, distilled water was added to adjust the final mass to 5.0 kg. The product was then cooled to near the gel temperature and extruded through a small hole into chilled water, thereby creating a very fine noodle. These noodles were supplied as amplification catalysts for producing blue silver on site. For convenience and to prevent the noodles from forming a molten mass, the noodles were diluted with water to make water 1 to noodle 3.

6.5 g of potassium hydroquinone monosulfonate and 0.29 g of KCl dissolved in 81 g of distilled water were added to 650 g of borohydride-reduced silver nuclei. The noodle slurry was cooled to about 6 ° C. Moreover, two types of solutions (A) and (B) having the following compositions were prepared in separate containers.
(A) 19.5 g sodium sulfite (anhydrous), 0.98 g sodium bisulfite (anhydrous), 122.0 g distilled water (B) 9.75 g silver nitrate, 122.0 g distilled aqueous solution

  The above solutions (A) and (B) were mixed and stirring was continued to form a white precipitate. Immediately, this mixture was then added to the noodle slurry with rapid stirring in a short time (within 5 minutes). The temperature was maintained at 10 ° C. and amplification was allowed to proceed for about 80 minutes until all soluble silver salt was reduced onto the nuclei. The resulting blue slurry particles were washed through the slurry in a nylon mesh bag through the slurry and washed for about 30 minutes with the wash water passing through the bag so that all the salt was washed away. The blue silver dispersed and washed in the gel slurry was drained until the product mass was 412 g so as to obtain a blue silver dispersion having a concentration of 1.5% by weight silver when melted. Transmission electron micrographs showed that the silver consisted of particles with the particle sizes listed in the table.

Preparation of silver particle dispersion liquid To 4000 g of the silver dispersion slurry obtained as described above, 6 g of a dispersant (trade name: Rapisol B-90, manufactured by Nippon Oil & Fats Co., Ltd.) and 2000 g of papain 5% aqueous solution are added, and the temperature is increased. Stored at 37 ° C. for 24 hours. This liquid was centrifuged at 2000 rpm for 5 minutes to precipitate silver particles. After discarding the supernatant, it was washed with distilled water to remove the degradation product of gelatin decomposed by the enzyme. The silver particle sediment was then washed with methyl alcohol and dried. An aggregate of about 60 g of silver fine particles was obtained. 53 g of this aggregate, 5 g of a dispersant (trade name: Solsperse 20000, manufactured by Avicia Co., Ltd.), and 22 g of methyl ethyl ketone were mixed. This was mixed with 100 g of 2 mmφ glass beads and dispersed with a paint shaker over 3 hours to obtain the intended silver particle dispersion (A1).

The following additive was added to and mixed with the silver particle dispersion (A1) obtained above to obtain a silver particle-containing coating solution.
-40.0 g of the above silver particle dispersion (A1)
・ Propylene glycol monomethyl ether acetate 40.0g
・ Methyl ethyl ketone 37.6g
・ Fluorosurfactant 1 (trade name: F-780-F, manufactured by Dainippon Ink & Chemicals, 30% methyl ethyl ketone solution) 0.1 g
・ Hydroquinone monomethyl ether 0.001g
・ Dipentaerythritol hexaacrylate 2.1g
・ Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl)
Phenyl] carbamoyl] phenyl] sebacate 0.1 g

Preparation of coating solution for light shielding layer The carbon black dispersion obtained above and the silver particle-containing coating solution obtained above were added and mixed to prepare a coating solution for the light shielding layer. The coating solution for the light shielding layer was prepared to have a blend ratio of carbon black (CB) / silver particles shown in Table 2.

Production Method of Photosensitive Transfer Material A thermoplastic resin layer coating solution composed of the following formulation H1 was applied and dried on a 75 μm thick polyethylene terephthalate film temporary support using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the light shielding layer coating solution was applied and dried. In this way, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a light shielding layer are provided on the temporary support, and finally a protective film (12 μm thick polypropylene) is provided. Film).
In this way, a dark color photosensitive transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the light shielding layer were integrated was prepared, and the sample name was designated as photosensitive transfer material K1.

Coating liquid for thermoplastic resin layer: Formulation H1
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether acetate 6.36 parts ・ Methyl ethyl ketone 52.4 parts ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37 Molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (2,2-bis [4- (methacryloxypolyethoxy) Phenyl] propane, manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts. Fluorosurfactant 1 0.54 parts

Intermediate layer coating solution: Formulation P1
・ Polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550) 32.2 parts ・ Polyvinylpyrrolidone (trade name: K-30, manufactured by IP Japan)
14.9 parts ・ Distilled water 524 parts ・ Methanol 429 parts

A silane coupling treated glass substrate was obtained using a glass substrate with a silane coupling agent solution (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd., 1% dilution).
The protective film is removed from the photosensitive transfer material produced by the above-described manufacturing method on the obtained silane coupling treated glass substrate, and the surface of the light shielding layer exposed after the removal and the surface of the silane coupling treated glass substrate are Using a laminator (trade name: Lamic II type, manufactured by Hitachi Industries, Ltd.), the substrate is covered with a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. Laminated. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and intermediate layer The distance between them was set to 200 μm, and pattern exposure was performed with an exposure amount of 200 mJ / cm ² .

Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) 12 times with pure water (1 part by mass of T-PD2 and pure water) The mixture was mixed at a ratio of 11 parts by mass (30 ° C.) and subjected to shower development with a flat nozzle at a pressure of 0.04 MPa for 50 seconds to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto the substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower to perform pure water shower cleaning, and air was blown to reduce the liquid pool on the substrate.
Subsequently, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and Stabilizer-containing; trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with pure water (29 ° C.) for 30 seconds, shower with cone type nozzle at pressure of 0.15 MPa Development was performed to develop and remove the photosensitive resin layer to obtain a pattern image.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) was diluted 10 times with pure water. The liquid (33 ° C.) was used as a shower with a cone type nozzle at a pressure of 0.02 MPa for 20 seconds, and the residue was removed by rubbing the pattern image with a rotating brush having nylon bristles to obtain a black matrix. .
Subsequently, the entire surface of the substrate from the surface of the substrate was post-exposed at 2 0 0 0 mJ / cm ² with an aligner in the atmosphere, and heat treatment was performed at 220 ° C. for 30 minutes to obtain the black matrix of Example 1.
Further, Examples 2 to 4 and Examples 7 and 8 were carried out in the same manner as Example 1 except that each coating solution for light shielding layer was prepared and used so as to have a blend ratio of carbon black / silver particles shown in Table 2. And 12 black matrices were obtained.

Production of color filter Production of photosensitive resin transfer material Photosensitive transfer material R, photosensitive transfer material, using the colored photosensitive resin composition shown in Table 1 below in the same manner as the production of photosensitive transfer material K1. Material G and photosensitive transfer material B were prepared.

Red (R) pixel formation Except that the exposure amount in the exposure process was changed to 40 mJ / cm ² , the shower development with a sodium carbonate-based developer was changed to 35 ° C. for 35 seconds, and the heat treatment was changed to 220 ° C. for 15 minutes. The same process as the formation of the black matrix was performed, and the photosensitive resin transfer material R was used to form red (R) pixels on the side of the glass substrate where the black shielding matrix was formed.
The thickness of the R pixel is 2.0 μm. I. Pigment Red (C.I.P.R.) 254, C.I. I. P. R. The coating amounts of 177 were 0.88 g / m ² and 0.22 g / m ² , respectively.
After that, the glass substrate on which the R pixel is formed is again cleaned with a brush using a cleaning agent as described above, shower-washed with pure water, and then 100% by a substrate preheating device without using a silane coupling liquid. Heated at 0 ° C. for 2 minutes.

Green (G) pixel formation Except that the exposure amount in the exposure process was changed to 40 mJ / cm ² , the shower development with a sodium carbonate-based developer was changed to 34 ° C. for 45 seconds, and the heat treatment was changed to 220 ° C. for 15 minutes. The same process as the formation of the R pixel was performed, and a green pixel (G pixel) was formed on the side of the glass substrate where the black matrix and the R pixel were formed, using the photosensitive resin transfer material G obtained above. .
The G pixel has a thickness of 2.0 μm. I. Pigment green (C.I.P.G.) 36, C.I. I. Pigment Yellow (C.I.P.Y.) each coating amount of 150 1.12g / m ^2, was 0.48 g / m ^2.
After that, the glass substrate on which the black matrix, R pixel, and G pixel are formed is again cleaned with a brush using a cleaning agent as described above, shower-washed with pure water, and without using a silane coupling liquid. It heated at 100 degreeC for 2 minute (s) with the board | substrate preheating apparatus.

Blue (B) pixel formation The same process as the R pixel formation was performed except that the exposure amount in the exposure process was changed to 30 mJ / cm ² and the shower development with a sodium carbonate-based developer was changed to 36 ° C. for 40 seconds. Using the photosensitive resin transfer material B obtained as described above, blue pixels (B pixels) were formed on the side of the glass substrate where the black matrix and R and G pixels were formed.
The thickness of the B pixel is 2.0 μm. I. Pigment Blue (C.I.P.B.) 15: 6, C.I. I. Pigment Violet (C.I.P.V.) each coating amount of 23 0.63g / m ^2, was 0.07 g / m ^2.
Thereafter, the glass substrate on which the R, G, and B pixels were formed was baked at 240 degrees for 50 minutes to obtain a color filter.

In Table 1, the composition of the binder 2 is as follows.
-Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27 parts-Propylene glycol monomethyl ether acetate 73 parts

The composition of the DPHA solution is as follows.
Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts Propylene glycol monomethyl ether acetate 24 parts The composition of R pigment dispersion 1 is as follows.
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 8 parts, 0.8 part of the following compound 1, polymer (benzyl methacrylate / methacrylic acid = 73/27 molar ratio)
Random copolymer) 8 parts ・ 83 parts of propylene glycol monomethyl ether acetate

Compound 1

The composition of R pigment dispersion 2 is as follows.
・ C. I. P. R. 177 (trade name: Cromophtal Red A2B, manufactured by Ciba Specialty Chemicals) 18 parts Polymer (random copolymer of benzyl methacrylate / methacrylic acid = 73/27 molar ratio) 12 parts Propylene glycol monomethyl ether acetate 70 Part

The composition of binder 1 is as follows.
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 38/25/37 molar ratio, molecular weight 40,000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts Additive 1 is a phosphate ester special activator ( Product name: HIPLAAD ED152, manufactured by Enomoto Kasei Co., Ltd.).

As the G pigment dispersion 1, GT-2 (trade name, manufactured by FUJIFILM Electronics Materials Co., Ltd.) was used.
As the Y pigment dispersion 1, CF Yellow EX3393 (trade name, manufactured by Mikuni Color Co., Ltd.) was used.
As the B pigment dispersion 1, CF Blue EX3357 (trade name, manufactured by Gokoku Color Co., Ltd.) was used.
As the B pigment dispersion 2, CF Blue EX3383 (trade name, manufactured by Mikuni Color Co., Ltd.) was used.

The composition of binder 3 is as follows.
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts

Examples 5 and 6
Formation of Black Matrix The light-shielding layer coating solution was prepared in the same manner as in Example 1 except that each light-shielding layer coating solution was prepared and used to have a carbon black / silver particle blend ratio shown in Table 2. A photosensitive light-shielding layer used in Examples 5 and 6 was formed by coating on a glass substrate and drying.
Next, a pattern exposure of 500 mJ / cm ² was performed on the photosensitive light-shielding layer using an ultrahigh pressure mercury lamp. Thereafter, as a developing solution, 0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% by mass sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer. The photosensitive black resin layer of the light-shielding layer is developed using a solution (29 ° C.) obtained by diluting a sodium carbonate developer (trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) 5 times with pure water. Then, the unexposed portion was removed, and the intended black matrices of Examples 5 and 6 were formed. Thereafter, the color filters of Examples 5 and 6 were produced in the same manner as Example 1.

Example 9
A color filter shown in Table 3 was prepared in the same manner as in Example 1 except that the “ silver particle-containing coating solution” used in Example 1 was changed to the following “silver / silver sulfide-containing light shielding layer coating solution”. .
Preparation of silver / silver sulfide core-shell particles Acetone dispersion of silver particles (average particle size 30 nm, concentration 2.5 mass%) and vinyl pyrrolidone / vinyl acetate copolymer (= 60/40 [mass ratio], molecular weight 5000) Was added and stirred for 30 minutes. Next, an aqueous solution of sodium sulfide (23 ° C.) having a concentration of 7.2% by mass was added to the mixture so that the sulfidation ratio of the metal was 30%, and after the addition was completed, the mixture was stirred for 30 minutes. Silver / silver sulfide core-shell particles having a shell of
Here, the sulfidation rate indicates the rate at which the metal particles are sulfided. A sulfidation rate of 0% represents a state that is not sulfided at all, and a sulfidation rate of 100% represents a state in which the entire particle is completely sulfided.

Example 10
Tin particles were produced in the same manner as in Example 1 except that tin particles were used instead of silver particles, and color filters shown in Table 3 were produced in the same manner as in Example 1.

Example 11
A color filter shown in Table 3 was produced in the same manner as in Example 1 except that the silver particle-containing coating solution was changed to the following silver-tin alloy-containing light shielding layer coating solution.
Preparation of AgSn alloy particle dispersion (dispersion A1) In 1000 ml of pure water, 23.1 g of silver (I) acetate, 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate, polyethylene glycol (molecular weight 3, 2) and 5 g of E735 (manufactured by ISP; vinylpyrrolidone / vinyl acetate copolymer) were dissolved to obtain a solution 1.
Separately, 36.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.

  While the solution 1 obtained above was vigorously stirred while maintaining at 25 ° C., the above solution 2 was added thereto over 2 minutes, and the mixture obtained by the addition was gently stirred for 6 hours. Then, the mixed solution turned black, and silver tin (AgSn) alloy fine particles were obtained. Next, the mixed solution was centrifuged to precipitate the AgSn alloy fine particles. In the centrifugation step, the mixed solution is subdivided into 150 ml portions, and is centrifuged at a rotational speed of 2,000 rpm by a tabletop centrifuge (trade name: H-103n, manufactured by Kokusan Co., Ltd.). For a minute. After the centrifugation, the supernatant in the sample was discarded to a total liquid volume of 150 ml. 1350 ml of pure water was added to the sample and stirred for 15 minutes to disperse the AgSn alloy fine particles again. This precipitation and dispersion operation was repeated twice to remove soluble substances in the aqueous phase.

  Thereafter, centrifugation was further performed to precipitate the AgSn alloy fine particles again. Centrifugation was performed under the same conditions as described above. After centrifuging, the supernatant was discarded as described above, the total liquid volume was made 150 ml, 850 ml of pure water and 500 ml of acetone were added thereto, and the mixture was further stirred for 15 minutes to disperse the AgSn alloy fine particles again.

  Centrifugation was performed again in the same manner as above to precipitate AgSn alloy fine particles, and then the supernatant was discarded as described above to a liquid volume of 150 ml, and 150 ml of pure water and 1200 ml of acetone were added thereto and stirred for another 15 minutes. The microparticles were dispersed again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid volume 70 ml, and 30 ml of acetone was added thereto. This was dispersed for 6 hours using an Eiger mill (trade name: M-50 type (media: diameter 0.65 mm zirconia beads 130 g), manufactured by Eiger Japan Co., Ltd.) to obtain a silver tin (AgSn) alloy fine particle dispersion It was. As a result of observing the fine particle dispersion with a transmission electron microscope, the dispersion average particle size was about 40 nm in terms of number average particle size.

Preparation of silver-tin alloy-containing light-shielding layer coating solution The following composition was mixed to prepare a silver-tin alloy-containing light-shielding layer coating solution.
-AgSn alloy particle dispersion (dispersion A1) 50.00 parts-Propylene glycol monomethyl ether acetate 28.6 parts-Methyl ethyl ketone 37.6 parts-Fluorosurfactant 0.2 parts-Hydroquinone monomethyl ether 0. 001 parts styrene / acrylic acid copolymer (molar ratio = 56/44, weight average molecular weight 30,000) 9.6 parts dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 6 parts bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.5 part

Comparative Examples 1-4
In the same manner as in Example 1, the amount of carbon black and silver particles added was adjusted, and color filters shown in Table 3 were produced.
TFT color reflectance, transmission optical density, transmission optical density per unit film thickness, R, G, B film thickness, film thickness ratio (TR / BM, TG / BM and TB / BM) in each color filter obtained The projection height, chromaticity, and display unevenness were measured, and the results are shown in Tables 2 and 3.

Production of liquid crystal display device ITO (Indium Tin Oxide) transparent electrodes were further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of each color filter substrate obtained from the above examples and comparative examples. . Next, according to Example 1 of Japanese Patent Application Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the partition wall (black matrix) on the ITO film formed as described above.
Separately, a glass substrate was prepared as a counter substrate. Patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped, and a counter substrate and Pasted together. The bonded substrate was irradiated with UV and then heat treated to cure the sealant. A polarizing plate (trade name: HLC2-2518, manufactured by Sanritz Co., Ltd.) was attached to both surfaces of the liquid crystal cell thus obtained. Subsequently, FR1112H (trade name, manufactured by Stanley Co., Ltd.) which is a chip type LED as red (R) LED, DG1112H (trade name, manufactured by Stanley Co., Ltd.) which is a chip type LED as green (G) LED, A side-light type backlight was configured using DB1112H (trade name, manufactured by Stanley Co., Ltd.), which is a chip-type LED, as a blue (B) LED. The backlight was placed on the side of the liquid crystal cell provided with the polarizing plate to form the liquid crystal display device.

Evaluation Method Film Thickness Measurement The film thickness was measured for each black matrix or colored pixel formed after baking using a contact-type surface roughness meter (trade name: P-10, manufactured by TENCOR). .
Transmission optical density measurement The transmission optical density of the black matrix was measured by the following method.
First, using the material in which the black matrix is formed in the examples and comparative examples, the ultra-high pressure mercury lamp is applied to the light-shielding layer coated on a thin film on the glass substrate so that the OD is 3.0 or less. An exposure of 500 mJ / cm ² was performed from the surface side. Next, the optical density (OD) was measured using a Macbeth densitometer (trade name: TD-904, manufactured by Macbeth). Separately, the transmission optical density (OD ₀ ) of the glass substrate was measured by the same method. Using a contact-type surface roughness meter (trade name: P-10, manufactured by KLA-Tencor Corporation), the film thickness of the measurement sample is measured, and the value obtained by subtracting OD ₀ from the above OD is transmitted through the light shielding layer. The optical density of the black matrix having the film thickness produced in the example was calculated from the relationship between the transmission optical density and the film thickness of the measurement result.

TFT side reflectance measurement Using an absolute reflectance measuring device (trade name: ARV-474, manufactured by JASCO Corporation) combined with a spectrophotometer (trade name: V-560, manufactured by JASCO Corporation). The absolute reflectance of the TFT side reflectance (surface on which the coating film is formed) was measured.
The measurement angle is 5 degrees from the vertical direction, and the wavelength is 555 nm.

Particle diameter (nm) measurement With a transmission electron microscope (trade name: JEM-2010, magnification 200000 times, manufactured by JEOL Ltd.), 100 particles were measured and converted into a circle having the same area as the projected area. The diameter was taken as the particle size, and the average value was taken as that value.

Measurement of chromaticity The chromaticity of the color filter obtained above was measured at a pinhole diameter of 5 μm using a microspectrophotometer (trade name: OSP100, manufactured by Olympus Optical Co., Ltd.). As calculated.
Display color mixing In Examples and Comparative Examples, red (R), green (G), and blue (B) were colored simultaneously, and density unevenness in a certain area (10 cm × 10 cm) range was determined with the naked eye. The determination is carried out by 10 persons, and when the number of persons determined to have density unevenness is zero, A is indicated as B, when the number is 1-2, X is indicated when the number is 3 or more. evaluated.

TFT malfunction A part of the backlight of the LCD is reflected on the surface of the black matrix layer and becomes incident light on the TFT, resulting in more light during black display. The presence of this light was evaluated as a malfunction. The presence or absence is shown in Tables 2 and 3. More light was evaluated by checking in the dark.
Display unevenness When a gray test signal was input to the liquid crystal display device, it was observed visually and with a magnifying glass to determine whether unevenness occurred.

LR※：液状レジスト使用による現像法

LR *: Development method using liquid resist

From the results of Tables 2 and 3, the following can be understood.
The color filter of the example has high transmission optical density even when the thickness of the black matrix is thin, high transmission optical density per unit film thickness, good chromaticity, no display unevenness, and low TFT side reflectance. Excellent contrast.

  The color filter for a liquid crystal display device and the liquid crystal display device of the present invention are excellent in display contrast in a bright room, have no TFT malfunction, have no display unevenness, and can achieve both high color purity and high transmittance.

Claims (12)

A color filter for a liquid crystal display device comprising a transparent substrate and a black matrix provided on the transparent substrate,
Including G (green) colored pixels in a region to be separated of the black matrix;
A part of the colored layer of the G (green) colored pixel is laminated on a part of the black matrix;
The black matrix is selected from a pigment , metal particles selected from gold, silver, copper, platinum, palladium, and tin , and metal alloy particles containing these metals , and gold, silver, copper, platinum, and palladium. to contain at least one selected from the metal compound particles containing a metal;
The ratio (B / A) of the content B of the pigment to the content A of the metal particles (including metal alloy particles) and metal compound particles in the black matrix (B / A) is in the range of 0.2 to 10; A film thickness ratio (TG / BM) between a film thickness TG of a (green) colored pixel and a film thickness BM of a black matrix is in a range of 1.2 to 10, wherein the color filter for a liquid crystal display device . An R (red) colored pixel and a B (blue) colored pixel are further included in a region to be separated from the black matrix;
The film thickness ratio (TR / BM) between the film thickness TR of the R (red) colored pixel and the BM is in the range of 1.2 to 10; and the film thickness TB of the B (blue) colored pixel 2. The color filter for a liquid crystal display device according to claim 1, wherein a film thickness ratio (TB / BM) between the BM and the BM is in a range of 1.2 to 10. 5.   The protruding portion formed by laminating a part of the colored layer of the colored pixel on a part of the black matrix has a height protruding from the colored pixel of 0.4 μm or less. The color filter for a liquid crystal display device according to claim 1 or 2.   The color filter for a liquid crystal display device according to claim 1, wherein the black matrix has a transmission density of 3.5 or more and a film thickness of 1.3 μm or less.   The chromaticity point on the CIE chromaticity diagram of the G (green) C light source described above is in a chromaticity range of G (x ≦ 0.32, y ≧ 0.56). The color filter for liquid crystal display devices of any one of 1-4.   The chromaticity point on the CIE chromaticity diagram by the C light source of the three primary colors R (red), G (green), and B (blue) described above is R (x ≧ 0.62, y ≦ 0.35). , G (x ≦ 0.32, y ≧ 0.56), and B (x ≦ 0.17, y ≦ 0.14) in the chromaticity range. Item 1. A color filter for a liquid crystal display device according to item 1.   The color filter for a liquid crystal display device according to claim 1, wherein the pigment contains at least one selected from carbon black and graphite. The color filter for a liquid crystal display device according to any one of claims 1 to 7, wherein the metal particles (including metal alloy particles) or metal compound particles contained in the black matrix are metal particles. . The metal particles (including metal alloy particles) or metal compound particles contained in the black matrix include at least one selected from Ag fine particles , AgSn alloy fine particles , silver sulfide fine particles, and tin fine particles. The color filter for liquid crystal display devices of any one of Claims 1-7. The said black matrix contains the photosensitive resin composition containing at least 1 selected from the said pigment and the said metal particle (a metal alloy particle is included) and a metal compound particle, The Claim 1-9 characterized by the above-mentioned. The color filter for liquid crystal display devices of any one. The black matrix includes a photosensitive transfer material containing at least one selected from the pigment and the metal particles (including metal alloy particles) and metal compound particles. A color filter for a liquid crystal display device according to claim 1.   A liquid crystal display device comprising the color filter for a liquid crystal display device according to claim 1.

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