KR20080025097A - Color filter and liquid crystal display device using same - Google Patents

Abstract

Provided is a color filter for a liquid crystal display device, which includes a transparent substrate and a black matrix arranged on the transparent substrate. The color filter is characterized in that a G (green) color pixel is included in an area demarcated by the black matrix; a part of a color layer of the G (green) color pixel is laminated on a part of the black matrix; the black matrix contains a pigment and at least one kind of particles selected from metal particles and a metal compound particles; a ratio (B/A) of a contained amount (B) of the pigment to a contained amount (A) of the metal particles and the metal compound particles in the black matrix is within a range of 0.2-10; and a film thickness ratio (TG/BM) of the film thickness (TG) of the G (green) color pixel to the black matrix film thickness (BM) is within a range of 1.2-10. A liquid crystal display device which includes such color filter is also provided. ® KIPO & WIPO 2008

Description

COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE USING SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter and a liquid crystal display device for a liquid crystal display device. In particular, a liquid crystal display device having excellent display contrast, no malfunction of TFTs, no display unevenness, and capable of achieving both high color purity and high transmittance. The present invention relates to a color filter for liquid crystal and a liquid crystal display device.

In the color filter used for a color liquid crystal display or the like, colored pixels R, G, and B are formed on a transparent substrate, and display contrast is provided in a gap between each of the colored pixels of R (red), G (green), and B (blue). For the purpose of improvement of the black matrix, a black matrix is formed. In particular, in addition to the above object, the black matrix used in the liquid crystal display device of the active matrix driving method using the thin film transistor (TFT) has a high difference in order to prevent the deterioration of the image quality caused by the current leakage caused by the light of the thin film transistor. Luminance is required.

As a well-known example of the formation method of the black matrix which uses a metal film, such as chromium, as a light shielding layer, a metal thin film is produced by a vapor deposition method or a sputtering method, a photoresist is apply | coated on the said metal thin film, and then the black matrix The method includes exposing and developing a photoresist layer through a photomask having a pattern, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film (eg, "color TFT Liquid Crystal Monitor "218-220 pages (Kyoritsu Publication, 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 step such as a vapor deposition method or a sputtering method or an etching step is required, and the cost is high and the load on the environment cannot be ignored. In addition, since this method is a metal film, the reflectance is increased to cause malfunction of the TFT or to reduce the contrast in bright room. For these problems, a means of using a low-reflection chromium film (such as two layers of metal chromium and chromium oxide) can be devised, but it can not be denied that the cost increases further.

Moreover, as another well-known example of the formation method of a black matrix, the method of using the photosensitive resin composition containing a light-shielding pigment (for example, carbon black) is also known. In this so-called self-aligning black matrix forming method, after forming each pixel of R, G, and B on a transparent substrate, carbon black containing photosensitive resin composition is apply | coated on this pixel, and R, G of the said transparent substrate is carried out. And exposing to the entire surface from the B pixel non-forming surface side (for example, Japanese Patent Application Laid-Open No. 62-9301).

Although the manufacturing cost is low compared with the method by etching the said metal film, this method requires about 1.1-1.4 micrometers of film thicknesses required in order to acquire sufficient light-shielding property (for example, OD = 4.0). As a result of the problem of increasing the film thickness, overlapping (stepping) of the black matrix and each pixel of R, G, and B occurs, flatness of the color filter deteriorates, and unevenness in the cell gap of the liquid crystal display device. Occurs, leading to poor display such as color unevenness.

Therefore, in order to obtain a film with a thin thickness and high OD, the technique of manufacturing the light shielding film for black-matrix manufacture using the photosensitive resin composition containing a metal particle is proposed (Japanese Patent Laid-Open No. 2004-240039).

Moreover, in order to make the color taste of a black matrix close to black, the black matrix which has a light shielding film containing a metal particle and pigment microparticles | fine-particles is 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 gloss, and thus there is a problem that the clear room contrast decreases when the color filter is produced using the black matrix. Moreover, when there is much content of the black pigment microparticles | fine-particles in a black matrix, thinning of a black matrix becomes difficult and the thickness of a black matrix becomes thick. As a result, superimposition (step) of the black matrix and the R, G, and B (red, green, and blue) pixels occurs, flatness of the color filter deteriorates, and cell gaps of the liquid crystal display elements occur, resulting in display defects such as color irregularities. Leads to.

Non-Patent Document 1: 218-220 pages of "Color TFT Liquid Crystal Display" (Kyoritsu Publishing Co., Ltd., published April 10, 1997)

Patent Document 1: Japanese Patent Application Laid-Open No. 62-9301

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-240039

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-317897

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

The said object of this invention is achieved by providing the color filter for liquid crystal display devices and liquid crystal display devices which consist of the following structures.

(1) A color filter for a liquid crystal display device comprising a transparent substrate and a black matrix formed on the transparent substrate:

A black (green) colored pixel in a region partitioned by the black matrix;

A part of the colored layer of said G (green) colored pixel is laminated on a part of said black matrix;

The black matrix contains a pigment and at least one selected from metal particles and metal compound particles;

The ratio (B / A) of the content B of the pigment to the content A of the metal particles and the metal compound particles in the black matrix is in the range of 0.2 to 10; Also

A film thickness ratio (TG / BM) of the film thickness TG of the G (green) colored pixel and the film thickness BM of the black matrix is in the range of 1.2 to 10, wherein the color filter for a liquid crystal display device.

(2) further comprising colored pixels of R (red) and colored pixels of B (blue) in a region partitioned by the black matrix;

The film thickness TR of the colored pixel of R (red) and the film thickness ratio TR / BM of the BM are in the range of 1.2 to 10; Also

The film thickness TB of the colored pixel of said B (blue) and the film thickness ratio (TB / BM) of said BM exist in the range of 1.2-10, The color filter for liquid crystal display devices of said (1) characterized by the above-mentioned.

(3) The liquid crystal as described in said (1) or (2) characterized by the height which protrudes with respect to the colored pixel of the processus | protrusion part by which one part of the colored layer of a colored pixel was laminated | stacked on a part of said black matrix, or less. Color filter for display devices.

(4) The color filter for liquid crystal display devices according to any one of (1) to (3), wherein the black matrix has a transmission density of 3.5 or more and a film thickness of 1.3 µm or less.

(5) In the above (1) to (4), 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 devices of any one of Claims.

(6) The chromaticity points on the CIE chromaticity diagram of three primary colors of R (red), G (green), and B (blue) described above are R (x ≧ 0.62, y ≦ 0.35), and G (x ≦ 0.32, y≥0.56) and B (x≤0.17, y≤0.14) It exists in the chromaticity range, The color filter for liquid crystal display devices in any one of said (2)-(5) characterized by the above-mentioned.

(7) The color filter for 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 filter or metal compound particle contained in the said black matrix is a metal particle, The color filter for liquid crystal display devices in any one of said (1)-(7) characterized by the above-mentioned.

(9) The liquid crystal display according to any one of (1) to (7), wherein the metal particles or metal compound particles contained in the black matrix contain at least one selected from Ag fine particles and AgSn alloy fine particles. Color filter for the device.

(10) Said black matrix contains photosensitive resin composition containing the said pigment and at least 1 selected from the said metal particle and a metal compound particle, The said any one of said (1)-(9) characterized by the above-mentioned. Color filter for liquid crystal display device.

(11) Said black matrix contains the pigment and the photosensitive transfer material containing at least 1 chosen from the said metal particle and a metal compound particle, The said any one of said (1)-(10) characterized by the above-mentioned. Color filter for liquid crystal display device.

(12) The liquid crystal display device containing the color filter for liquid crystal display devices in any one of said (1)-(11).

By the color filter and liquid crystal display device for liquid crystal display devices of this invention, the display contrast in a bright room is high, there is no malfunction of TFT, there is no display unevenness, and high color purity and high transmittance can be made compatible.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows one Embodiment of the thickness of the colored pixel and the height of a projection part in a comparative example.

It is explanatory drawing which shows another embodiment of the thickness of the colored pixel in this invention, and the height of a projection part.

The color filter for liquid crystal display devices of this invention has a black matrix on a transparent substrate. At least G (green) colored pixels are included in the region partitioned by the black matrix. A part of the colored layer of the said G (green) colored pixel is laminated | stacked on the one part on the said black matrix. The black matrix comprises 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 the metal compound particles and the content B of the pigment is 0.2 or more and 10 or less. 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 structural requirements of the color filter for liquid crystal display devices of this invention are demonstrated in detail. However, this invention is not limited to these description matters.

In the present invention, the black matrix contains at least one of a pigment, and metal particles and metal compound particles. They are contained in the black matrix at least in a dispersed state in the polymer compound.

The metal particle used by this invention is not specifically limited, Any thing may be used. Examples of preferred metals that the metal particles contain as their main components include metals selected from the group consisting of the fourth, fifth, and sixth periods of the periodic table of elements, and Groups 8, 9, 10, and 10 Metals selected from the group consisting of Group 11, Group 12, Group 13 and Group 14 are included. Among these metals, metals classified into the fourth, fifth, or sixth cycles, and further classified into Group 10, Group 11, or Group 12 are more preferable, and include gold, silver, copper, platinum, or Palladium is more preferred. Especially, gold, silver, and copper are especially preferable, and silver is especially preferable. Most preferably, the silver contained in the metal particles of the present invention is colloidal silver. In the production of metal particles, two or more kinds of the above metals may be used in combination. Moreover, it can also be used as an alloy which consists of 2 or more types of said metals for manufacture of metal particle.

Commercially available metal particles can be used. The metal particles can also be produced by chemical reduction of metal ions, electroless plating, evaporation of metals, or the like.

Examples of the method for preparing silver fine particles (colloidal silver) include a method for reducing soluble silver salts with hydroquinone in an aqueous solution of gelatin described in US Pat. No. 2,688,601, and the poorly soluble silver salt described in German Pat. To chemically reduce silver ions in solution, such as the method of reducing by hydrazine to silver by tannic acid described in US Pat. No. 2,921,914, Japanese Patent Application Laid-Open No. 5-134358 Conventionally known methods such as a method of forming silver particles by the electroless plating described, a method of evaporating a bulk metal into an inert gas such as helium, and a cold trap with a solvent This includes. In addition, examples of the method for producing silver fine particles (colloidal silver) include a method for producing yellow colloidal silver by a dextrin reduction method of Carey Le described in Colloidal Elements of Wiley & Sons, New York, 1933, Weiser.

The "metal compound" used in this invention is a compound of the said metal and elements other than a metal. Examples of compounds of metals and other elements include oxides, sulfides, sulfates, carbonates, and the like of metals. Of these, sulfides are particularly preferred because they easily form color or fine particles. Examples of these metal compounds include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), titanium black and the like. Among these, silver sulfide is particularly preferable in view of color tone, ease of particle formation, and stability.

Examples of the metal compound particles referred to in the present invention include the following ones.

(1) Fine particles composed of the metal compound

(2) Fine particles in which two or more kinds of metal compound particles are combined to form one particle

(3) fine particles comprising metal particles and metal compound particles

Specific examples of the fine particles in which two or more kinds of metal compound particles are combined include composite fine particles of silver and silver sulfide, composite fine particles of copper sulfide and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.

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, composite fine particles of silver and copper (II) oxide, and the like.

There is no restriction | limiting in particular in the shape of a composite fine particle. Examples of the shape include a shape having a different composition in the interior and the surface of the particle, a shape in which two kinds of particles are combined, and the like.

There is no restriction | limiting in particular in the particle diameter of a metal particle and / or a metal compound particle used by this invention. The average particle diameter is preferably in the range of 10 to 3000 nm, more preferably in the range of 30 to 2000 nm, and still more preferably in the range of about 60 to 200 nm. However, in the case of the metallic compound particles (not composite fine particles) of the above (1), the average particle diameter is less than 60 nm may be slightly poor in color tone. In addition, it is not preferable that particle diameter exceeds 3000 nm from a dispersible point.

There is no restriction | limiting in particular also about the particle diameter distribution of a metal particle and / or a metal compound particle.

The metal particles and / or metal compound particles used in the present invention need to be colored in order to obtain the required optical density. Here, colored means that optical absorption is shown in the wavelength range of 400-700 nm. Examples of colored metal compounds include silver 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 of this invention. Examples of the particle shape that can be used include spherical shape, irregular shape, plate shape, cube, octahedron, columnar shape and the like.

If necessary, two or more kinds of metal particles and / or metal compound particles having different compositions, shapes, particle diameters, and optical absorption wavelength ranges can be mixed and used.

In addition, the manufacturing method of a metal particle is described, for example in "the latest trend II in the technique and application of ultra-fine particle | grains (Jupeu Techno Research Co., Ltd., 2002).

Pigment

In the present invention, particularly black pigment fine particles are preferably used as the pigment. As an example, Pigment Black 7 (carbon black CINo.77266, for example, a brand name: Mitsubishi carbon black MA100 (made by Mitsubishi Kagaku Co., Ltd.), a brand name: Mitsubishi carbon black # 5 (made by Mitsubishi Kagaku Co., Ltd.)) , Black Pearls 430 (manufactured by Cabot Co.), graphite, etc. Among these, carbon black and graphite are particularly preferable.

The average particle diameter of the metal particle and pigment fine particle in this invention measures 50 particle diameters by observation with a transmission electron microscope (TEM), and calculates the average value.

The ratio (mass ratio B / A) of the amount A of the metal particles and / or the metal compound particles and the amount B of the pigment contained in the black matrix constituting the color filter of the present invention is in the range of 0.2 to 10, preferably 0.3 It exists in the range of -6.0, More preferably, it exists in the range of 0.8-5.0. When the said mass ratio B / A is less than 0.2, since the addition amount of the metal particle and / or metal compound particle in a black matrix is large, the reflectance of a black matrix becomes high, and therefore malfunction of TFT becomes easy to occur. On the other hand, when the said mass ratio B / A exceeds 10, since there are few metal particles and / or metal compound particles in a black matrix, in order to maintain the predetermined transmission optical density, the transmission optical density of a black matrix falls. It is necessary to thicken the black matrix. As a result, overlapping (stepping) of the black matrix and the pixels of R, G, and B occurs, so that flatness of the color filter is deteriorated and nonuniformity occurs in the cell gap of the liquid crystal display element. This nonuniformity tends to lead to display defects, such as a color nonuniformity, in the liquid crystal display device of this invention.

In addition, among the RGB pixels constituting the color filter of the present invention, the film thickness ratio TG of the G (green) colored pixel having the highest visibility and the film thickness ratio TG / BM of the black matrix film thickness BM are 1.2 to It exists in the range of 10, Preferably it exists in the range of 1.4-5.0, More preferably, it exists in the range of 2.0-4.0. In addition, the film thickness ratios TR, BM, TG / BM, and TB / BM of the respective film thicknesses TR, TG, TB of the colored pixels R (red), G (green), and B (blue), and the film thickness BM of the black matrix are It is preferable that all are in the range of 1.2-10, It is more preferable that all these film thickness ratios are in the range of 1.4-5.0, It is still more preferable that all these film thickness ratios are in the range of 2.0-4.0.

Here, the film thickness of a colored pixel is as follows. That is, in FIG. 1, the film thickness of a colored pixel is the thickness of the flat part of the colored pixel 10, and refers to the thickness shown by Ha. (In FIG. 1, BM> Ha.) Moreover, in FIG. In this case, the film thickness of the colored pixel is the thickness of the flat portion of the colored pixel 12, and refers to the thickness expressed by Hc. (Hc> BM in FIG. 2).

In this invention, it is preferable that the height which protrudes with respect to the colored pixel of the projection part by which one part of the colored layer of the colored pixel G was laminated | stacked on the said black matrix part is laminated | stacked, and it is preferable that it is 0-0.4 micrometer. It is more preferable to exist in the range of 0.3 micrometer, and it is still more preferable to exist in the range of 0-0.2 micrometer. Here, the projection height of the projection portion on the black matrix is as follows. That is, in FIG. 1, projection height means the height (thickness) of the part which protrudes from the thickness of the flat part of the colored pixel 10 on black-matrix BM, and means the film thickness Hb of a projection part. In addition, in FIG. 2, projection height means the height (thickness) of the part which protrudes from the thickness of the flat part of the colored pixel 12, and means the film thickness Hd of a projection part. When the height (thickness) of the projection part of the colored pixel on a black matrix is larger than 0.4 micrometer, since the color nonuniformity by the disturbance of the liquid-crystal orientation by the thickness difference of the pixel which light passes may generate | occur | produce, it is unpreferable.

It is preferable that the permeation density | concentration of a black matrix exists in the range of 3.5-10.0, and the film thickness exists in the range of 0.1-1.3 micrometer. It is more preferable that the said permeation concentration is 3.8 or more and the said film thickness is 1.1 micrometers or less. It is further more preferable that the said permeation concentration is 4.0 or more, and the said film thickness is 1.0 micrometer or less. If the black matrix has a high transmittance density and is thin in a range in which the film thickness thereof can maintain sufficient light shielding, superimposition (step difference) between the black matrix and each pixel of R, G, and B is less likely to occur. This is improved. Therefore, since the nonuniformity by the cell gap of a liquid crystal display element hardly arises, display defects, such as a color nonuniformity, do not arise.

Examples of the means for controlling the permeation concentration and the film thickness of the black matrix within the above ranges include adjusting the mass ratio of the pigment and the metal particles and / or the metal compound particles in the black matrix to a predetermined range and the like.

Black matrix

It is preferable that the black matrix of this invention is formed from the resin composition which contains a pigment, a metal particle, and / or a metal compound particle, and contains the polymer used as a binder, a dispersion stabilizer, surfactant, etc. In particular, the black matrix is preferably formed of a photosensitive resin composition (hereinafter also referred to as "composition for producing black matrix") containing metal particles having photosensitivity. Examples of the photosensitive resin composition for imparting such photosensitivity include those described in paragraphs [0016] to [0022] and [0029] of JP-A-10-160926.

When metal particles such as silver colloid are used in the form of an aqueous product, the composition for preparing the black matrix is preferably a composition of a purchase system. Examples of such a composition for producing an aqueous black matrix include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and a preferred example of the commercially available composition is SPP-M20 (trade name, Toyo Kosei Kogyo Co., Ltd.) etc. are included.

The composition for preparing the black matrix may be prepared by adding a photopolymerizable compound, a photopolymerization initiator, a inhibitor, and the like.

Preferable examples of the photopolymerizable compound used in the composition for producing the black matrix include monomers or oligomers having an ethylenically unsaturated double bond and capable of addition polymerization by irradiation with light. Examples of such monomers or oligomers include compounds having at least one addition polymerizable ethylenically unsaturated group in a molecule and having a boiling point of 100 ° C. or higher at atmospheric 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, trimethylol ethane triacrylate, trimethylolpropane triacrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedioldi (meth) acrylate, trimethylolpropane Tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated.

Specific examples of the photopolymerizable compound include urethane acrylates described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193; Polyester acrylates described in JP-A-48-64183, JP-A-49-43191 and JP-A-52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are also included.

You may use the above monomer or oligomer individually by 1 type or in mixture of 2 or more types. As for content of the said photopolymerizable compound with respect to the total solid of the said composition for black matrix preparation, 5-50 mass% is common, and 10-40 mass% is especially preferable.

As an example of the photoinitiator used for the composition for black matrix manufacture of this invention, the bisinal poly ketaldonyl compound disclosed by US patent 2367660 specification, and the acyl inether compound described in US patent 2448828 specification are mentioned. , Aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2722512, multinuclear quinone compounds described in US Pat. No. 3046127 and 2951758, US Pat. Combination of described triarylimidazole dimers and p-aminoketones, benzothiazole compounds and trihalomethyl-s-triazine compounds described in Japanese Patent Application Laid-open No. 51-48516, US Pat. No. 4,393,850 Trihalomethyl-s-triazine Compounds Described in the specification, trihalomethyloxadiazoles described in US Pat. No. 4212976 And the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers are preferred. As for content of the said photoinitiator with respect to the total solid of the composition for black-matrix preparation, 0.5-20 mass% is common, and 1-15 mass% is especially preferable.

The composition for black matrix preparation in the present invention may 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 composition for black matrix preparation in this invention can be made to contain various additives, for example, a plasticizer, surfactant, an adhesion promoter, a ultraviolet absorber, a solvent, etc. as needed.

The composition for black matrix preparation in this invention is prepared as a coating liquid which melt | dissolved or disperse | distributed each solid component mentioned above in a solvent, apply | coats these to the surface, such as a board | substrate or a support body, and is used in order to form a colored resin layer. .

Examples of the organic solvent used in the preparation of the composition for preparing the 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. This includes.

The film thickness of the resin layer for black matrices (hereinafter also referred to as "light shielding layer") is the composition of the spacer part finally formed on the color filter and the film thickness in the black matrix forming step using the cell gap and the composition for producing the black matrix. It is decided in consideration of the reduction rate.

The composition for black matrix preparation in this invention can be apply | coated to the surface of a board | substrate or the support body mentioned later by a well-known method, and it can dry, and can form a photosensitive sheet (light shielding layer).

Examples of the application means of the composition for producing the black matrix include slit coaters, spinners, rotary coaters, roller coaters, curtain coaters, knife coaters, wire bar coaters, extruders, and the like. The formed coating layer can then be dried to obtain a photosensitive resin layer or a photosensitive transfer sheet.

Photosensitive transfer material

In the present invention, a photosensitive transfer material can be produced using the pigment for producing a black matrix having the above photosensitivity, a metal particle and / or a metal compound particle-containing composition, and a black matrix can be produced using the above photosensitive transfer material. . The said photosensitive transfer material forms the photosensitive light shielding layer which consists of a composition for black-matrix creation containing the pigment | dye and metal particle which have said photosensitive property, and / or metal compound particle on the branch body at least. It is preferable that the film thickness of this photosensitive light shielding layer exists in the range of about 0.3-3.0 micrometers, and it is more preferable that it exists in the range which is about 0.5-2.0 micrometers.

The photosensitive transfer material may have a structure basically the same as that of a known photosensitive transfer material, except that the above-mentioned photosensitive pigment and metal particles and / or metal compound particle-containing compositions are used as the photosensitive resin material. Examples of the configuration of known photosensitive transfer materials are described in JP-A-5-173320. The most basic configuration of such a photosensitive transfer material includes a sheet of a sheet made of a flexible plastic film or the like and a thin layer made of a composition for preparing a black matrix formed on the sheet sheet. An undercoat layer or an intermediate layer, such as a layer for facilitating peeling therebetween, a layer serving as a cushion for the light shielding layer, or the like can be arbitrarily formed between the support sheet and the light shielding layer. Examples of the preferred configuration include a configuration in which an alkali-soluble thermoplastic resin layer, an intermediate layer, and a light shielding layer are formed on a support sheet. On the light shielding layer, a protective film may be further arbitrarily laminated.

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

In the process of producing the photosensitive transfer material of the present invention, a solution of the composition for preparing a black matrix containing the metal particles having the photosensitivity of the present invention on a support, for example, a slit coater, a spinner, a rotation coater, a roller coater, a curtain A coating and drying process may be included using a coating means such as a coater, knife coater, wire bar coater, or extruder. When forming the layer of said alkali-soluble thermoplastic resin, the said alkali-soluble thermoplastic resin layer can also be manufactured by the same process.

Since the photosensitive transfer material of this invention forms the photosensitive light shielding layer which consists of a pigment, a metal particle, and / or a metal compound particle containing composition as mentioned above, it uses the said transfer material, and is light-shielded with high optical density in a thin film The layers can be formed to produce a black matrix.

Fabrication of the Black Matrix

The black matrix of the present invention is formed from the above-mentioned (photosensitive) pigment particles and metal particles and / or metal compound particle-containing compositions or light shielding layers produced using the photosensitive transfer material having the composition. The film thickness of the black matrix is generally about 0.1 to 1.3 mu m. Since the black matrix of the present invention uniformly disperses pigment particles and metal particles and / or metal compound particles, even a thin film having a film thickness within the above range can exhibit sufficient optical density (shielding performance).

An example of a method of producing a black matrix using a photosensitive pigment particle and a metal particle and / or a metal compound particle-containing composition is to have a photosensitivity on a light-transmissive substrate and to apply the metal particle and / or metal compound particle-containing composition to The method of forming a black matrix by exposing through the photomask for black matrices by a conventional method, and developing after that to the layer (light shielding layer) formed, etc. are included. The coating method at the time of producing the said photosensitive transfer material can be similarly applied to the method of apply | coating the said metal particle and / or metal compound particle containing composition.

Moreover, when a pigment particle and a metal particle and / or a metal compound particle containing composition do not have photosensitivity, it is developable on the layer formed by apply | coating a pigment particle and a metal particle and / or a metal compound particle containing composition to a light transmissive substrate. A black matrix can be formed by forming a layer from the photosensitive resin composition, exposing through a photomask for black matrices by a conventional method, then developing and etching.

In the method for producing a black matrix using the photosensitive transfer material, the photosensitive transfer material is disposed on the light transmissive substrate so that the photosensitive light shielding layer of the photosensitive transfer material is in contact with each other, and then the photosensitive transfer material and the light transmissive substrate are laminated. The base member is peeled from the sieve, and then the photosensitive light-shielding layer is exposed through a black matrix photomask, and then developed to form a black matrix. As such, the method for producing the black matrix of the present invention does not require a cumbersome process, and is simple and inexpensive.

Coloring Compositions and Pigments

Next, the composition for colored pixels used for the color filter of this invention is demonstrated.

Examples of the composition which can be used as the color composition for color filters of the present invention include the compositions described in paragraphs [0046] to [0056] of JP-A-2004-347831.

Among the said pigments, it is preferable that the R (red) pixel of the color filter for liquid crystal display devices of this invention contains at least C.I. pigment red 254 (C.I.PR-254) as a pigment from a viewpoint of obtaining high color purity and flatness.

In addition, the G (green) pixel of the color filter of the present invention has at least CI pigment green 36 (CIPG-36) and CI pigment yellow 138 (CIPY-138) as a pigment from the viewpoint of obtaining high color purity and flatness. ), CI pigment yellow 139 (CIPY-139), CI pigment yellow 150 (CIPY-150) preferably contains any one.

In addition, the B (blue) pixel of the color filter of the present invention preferably contains at least C.I. Pigment Blue 15: 6 (C.I.PB-15: 6) as a pigment from the viewpoint of obtaining high color purity and flatness.

The pigment system can achieve high color purity in the permeable region on the long wave side. Moreover, the dispersibility and stability of a pigment are favorable, and it has a physical property suitable for the color filter use for liquid crystal display devices of this invention.

In the pigment composition of this invention, it is preferable that content of the said coloring agent (pigment) exists in the range of 0.1-70 mass% with respect to the total solid mass of a composition, It is more preferable to exist in the range of 0.5-60 mass%, It is especially preferable to exist in the range of 1.0-50 mass%.

By selecting the pigment system as described above, the chromaticity point on the CIE chromaticity diagram of three primary colors of R (red), G (green), and B (blue) is G (x≤0.32, y≥0.56). Preferred color filters for preferred liquid crystal display devices, more preferably satisfying R (x? 0.62, y? 0.35), G (x? 0.32, y? 0.56), and B (x? 0.17, y? 0.14) You can get it. Thereby, the HDTV standard which is the main chromaticity standard for TV use, without degrading the utilization efficiency of backlight light, ie, R (x = 0.64, y = 0.33), G (x = 0.3, y = 0.6), B (x High color purity can be further realized so as to exceed 0.15, y = 0.06).

Examples of the method for measuring the chromaticity point on the CIE chromaticity diagram by the C light source of the color filter include measuring each pixel formed on the transparent substrate using a microscopic spectrophotometer, or manufacturing pixels having a size of about 3 cm in all directions. And the method of measuring with a normal ultraviolet visible spectrophotometer, etc. are included.

In this invention, it is preferable that a preferable pigment is used in the state of a dispersion liquid. Examples of such dispersions include dispersions described in paragraphs [0058] to [0059] of JP-A-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 the light transmissive substrate, and each pixel constituting the pixel group is divided by a black matrix. The said black matrix is produced using the coloring composition for black matrix preparation of this invention, or the photosensitive transfer material of this invention. These at least three types of pixel groups of red, green, and blue are preferably arranged in a mosaic, stripe, triangle, or the like.

Examples of the light-transmitting substrate include known glass plates or plastic films such as a soda glass plate, a low-expansion glass plate, a non-alkali glass plate, a quartz glass plate and the like having a silicon oxide film on its surface.

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 transparent substrate by a conventional method. Alternatively, the method may include forming a black matrix first and then forming two or more pixel groups. Since the color filter of this invention is equipped with the black matrix as mentioned above, it has high display contrast and excellent flatness.

EMBODIMENT OF THE INVENTION Below, the manufacturing method of the color filter of this invention is demonstrated in detail. The color filter of this invention can be manufactured for every pixel of R, G, and B. Examples of this manufacturing method may include performing each of the following steps sequentially.

(1) a step of forming a photosensitive colored resin layer by bonding a photosensitive sheet composed of a color composition for preparing a color filter containing a photopolymerizable compound, a photopolymerization initiator, a binder, a coloring component (pigment) and the like on a substrate;

(2) exposing the photosensitive colored resin layer in a pattern;

(3) Process of developing exposed photosensitive colored resin layer and obtaining patterned colored cured film layer comprised from the exposure part of photosensitive colored resin layer; And

(4) The schedule which bakes and hardens further by heating the said patterned colored cured film layer.

The steps (1) to (4) can be carried out in the same manner as described in paragraphs [0062] to [0065] of JP-A-2004-347831.

Liquid crystal display

At least one of the embodiments of the liquid crystal display device of the present invention includes at least one of a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method or an active matrix driving method) between a pair of optically transparent substrates. It is equipped. The color filter has a pixel group of at least three colors. Each pixel constituting the pixel group is divided by the black matrix of the present invention. Since the color filter of this invention has high flatness, the cell gap does not generate | occur | produce between a color filter and a board | substrate in the liquid crystal display device provided with this color filter. Therefore, display defects, such as a color nonuniformity, do not arise.

Moreover, in another embodiment of the liquid crystal display device of this invention, at least 1 is equipped with at least a color filter, a liquid crystal layer, and liquid crystal drive means between a pair of light transmissive board | substrates. The liquid crystal drive means has an active element (for example, a TFT), and is provided with a color filter in which the pixel group of the three colors of the present invention and the black matrix are formed between each active element.

In addition, a preferred example of the liquid crystal display device according to the present invention using the color filter of the present invention has a three wavelength light source, by combining a backlight and the pixels of the three primary colors of R (red), G (green), and B (blue) Have Here, in the liquid crystal display device of the present invention, the chromaticity point on the CIE chromaticity diagram of three primary colors of R (red), G (green), and B (blue) is R (x ≧ 0.62, y ≦ 0.35) It is preferable to be in the chromaticity range of G (x ≦ 0.32, y ≧ 0.56) and B (x ≦ 0.17, y ≦ 0.14).

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these examples. In addition, "part", "%", and "molecular weight" in a present Example mean the "mass part", the "mass%", and the "mass average molecular weight" unless there is particular notice.

Example 1

Preparation of Carbon Black Dispersion

The dispersion of the carbon black of the following prescription was produced using the zirconia beads of 0.65 mm in diameter by the motor mill (brand name: M50, Eiger Co., Ltd. product).

Normal propanol 69 parts

10 parts of methacrylic acid / allyl methacrylate copolymer (copolymerization ratio = 20: 80)

Dispersant (trade name: Sol Spath 20000, manufactured by Avecia Co., Ltd.)

Carbon black (trade name: Carbon Black MA100, manufactured by Mitsubishi Chemical Corporation) 20 parts

Production of silver particles

3488 g of distilled water was added to 112 g of gelatin, and the obtained mixture was heated to about 47 DEG C to dissolve the gelatin. 4.0 g of calcium acetate and 2.0 g of potassium hydrogen boride were added thereto. Immediately thereafter, acetic acid dissolved in 1.0 L of distilled water was added while rapidly stirring 6.0 g. Further distilled water was added and the final mass was adjusted to 5.0 kg. The product was then cooled to near the gelling temperature and extruded into cooled water through a small hole, thereby producing a very fine noodle. Their noodle was fed as an amplification catalyst to produce blue silver in situ. For convenience, to prevent the noodle from forming a molten mass, the noodle was diluted with water to 1 water to noodle 3.

To 650 g of hydrogen boron-reduced silver core, 6.5 g of monosulfonic acid hydroquinone potassium and 0.29 g of KCl dissolved in 81 g of distilled water were added. The noodle slurry was cooled to about 6 ° C. In addition, two kinds of solutions (A) and (B) having the following composition were prepared in a container separately.

(A) 19.5 g sodium sulfite (anhydrous), 0.98 g sodium bisulfite (anhydrous), 122.0 g distilled water

(B) 9.75 g silver acetate, 122.0 g distilled water solution

The above solutions (A) and (B) were mixed and stirring continued to form a white precipitate. Immediately, the mixture was added to the noodle slurry with rapid stirring for a short time (within 5 minutes). The temperature was kept at 10 ° C. and amplification was allowed to proceed for about 80 minutes until all of the soluble silver salts were reduced on the nucleus. The obtained blue slurry particles were washed with a tap water through a slurry into a nylon mesh bag, and washed with water for about 30 minutes through the bag, so that all salts could be washed away. When the blue silver, which had been dispersed and washed in the gel slurry, was melted, the blue silver having a concentration of 1.5% by mass of silver was drained until the mass of the product became 412 g to obtain a dispersion. Transmission electron micrographs showed that this silver consists of particles of the particle diameters described in the table.

Preparation of Silver Particle Dispersion

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 Holding Co., Ltd.) and 2000 g of papain 5% aqueous solution were added, and stored at 37 ° C. for 24 hours. The solution was centrifuged at 2000 rpm for 5 minutes and the silver particles were allowed to settle. The supernatant was discarded and washed with distilled water to remove the enzyme-degraded gelatin digest. The silver particle precipitate 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 dispersing agent (trade name: Solfas 20000, manufactured by Avecia Co., Ltd.), and 22 g of methyl ethyl ketone were mixed. 100 g of 2 mm diameter glass beads were mixed with this, and it disperse | distributed over 3 hours with the paint shaker, and the target silver particle dispersion (A1) was obtained.

The following additive was added and mixed with the silver particle dispersion (A1) obtained above, and the silver particle containing coating liquid was obtained.

40.0 g of the silver particle dispersion (A1) described above

Propylene glycol monomethyl ether acetate 40.0 g

Methyl ethyl ketone 37.6 g

0.1 g of fluorine-based surfactant 1 (trade name: F-780-F, manufactured by Dainippon Ink Chemical Co., Ltd., 30% methyl ethyl ketone solution)

Hydroquinone monomethyl ether 0.001 g

Dipentaerythritol hexaacrylate 2.1 g

Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin 2-yl)

Phenyl] carbamoyl] phenyl] sebacate 0.1 g

Preparation of coating liquid for light shielding layer

The carbon black dispersion liquid obtained above and the silver particle containing coating liquid obtained above were added and mixed, and the coating liquid for light shielding layers was manufactured. The said light shielding layer coating liquid was manufactured so that it might become the mixing ratio of carbon black (C.B.) / silver particle shown in Table 2.

Preparation of Photosensitive Transfer Material

On the 75-micrometer-thick polyethylene terephthalate film support body, the coating liquid for thermoplastic resin layers which consists of following formula H1 was apply | coated and dried using the slit-shaped nozzle. Next, the coating liquid for intermediate | middle layers which consists of following prescription P1 was apply | coated and dried. Furthermore, the said light shielding layer coating liquid was apply | coated 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 were formed on the support and finally a protective film (thickness 12 μm polypropylene film) was pressed.

In this way, the dark photosensitive transfer material which integrated the support body, the thermoplastic resin layer, the intermediate | middle layer (oxygen barrier film), and the light shielding layer was produced, and the sample name was called photosensitive transfer material K1.

Coating liquid for thermoplastic resin layer: prescription 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.)

                                                               Part 5.83

13.6 parts of styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg ≒ 100 ° C.)

Compound (2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane produced by Shinnakamura Kagaku Kogyo Co., Ltd., dehydrated and condensed with 2 equivalents of pentaethylene glycol monomethacrylate to bisphenol A. Part 9.1

10.54 parts of fluorine-based surfactant

Intermediate Coating Solution: Prescription P1

32.2 parts of polyvinyl alcohol (trade name: PVA205, Clare Corporation, degree of saponification = 88%, degree of polymerization 550)

14.9 parts of polyvinylpyrrolidone (trade name: K-30, manufactured by ISP Japan)

524 parts of distilled water

Methanol 429 parts

The silane coupling process glass substrate was obtained using the silane coupling agent solution (brand name: KBM-603, the Shin-Etsu Chemical Co., Ltd. make, 1% dilution liquid) as a glass substrate.

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 is overlapped so as to be in contact with the surface of the silane coupling treated glass substrate. Brand name: Lamic II type | mold, the Hitachi Industries Co., Ltd. product) was used, and it laminated | stacked to the board | substrate at the rubber roller temperature of 130 degreeC, linear pressure 100N / cm, and conveyance speed 2.2m / min. Subsequently, the branched support of the polyethylene terephthalate was peeled off at the interface with the thermoplastic resin layer, and the branched support was removed. Proximity type exposure machine (manufactured by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) having ultra-high pressure mercury or the like, and the distance between the exposure mask surface and the intermediate layer in a state where the substrate and the mask (quartz exposure mask having an image pattern) are placed vertically. Was set to 200 µm, and the pattern was exposed to an exposure dose of 200 mJ / cm ² .

Next, triethanolamine-based developer (containing 30 mass% of triethanolamine, trade name: T-PD2, manufactured by Fujishashin Film Co., Ltd.) was purified 12 times with pure water (1 part by mass of T-PD2 and 11 parts by mass of pure water). The mixture was diluted with a liquid (30 ° C.) and shower-developed at a pressure of 0.04 MPa with a flat nozzle for 50 seconds to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto this substrate to remove the liquid, and then pure water was sprayed by a shower for 10 seconds, pure water shower cleaning was performed, and air was blown to reduce the amount of liquid accumulated on the substrate.

Next, Na carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5 mass% sodium dibutylnaphthalene sulfonate, anionic surfactant, an antifoamer, and stabilizer containing; brand name: T-CD1, The image development of the photosensitive resin layer was carried out by shower-development by pressure of 0.15 MPa with a cone nozzle for 30 seconds using the liquid (29 degreeC) diluted 5 times of Fujishashin Film Co., Ltd. with pure water.

Next, 20 seconds using the liquid (33 degreeC) which diluted the washing | cleaning agent (phosphate, a silicate, a nonionic surfactant, an antifoamer, and a stabilizer; brand name: T-SD1, Fujishashin Film Co., Ltd.) 10-fold with pure water 10 times, It sprayed as a shower with a cone nozzle at the pressure of 0.02 Mpa, and rubbed the pattern image with the rotary brush which has a nylon wool, and the residue was removed, and the black matrix was obtained.

Subsequently, in the air, the whole surface of the board | substrate was post-exposed at 2000 mJ / cm <^2> on the surface of a board | substrate with an aligner, the heat processing for 220 degreeC 30 minutes was performed, and the black matrix of Example 1 was obtained.

In addition, except that the coating liquid for each light shielding layer was prepared and used so that it might have a mixing ratio of carbon black / silver particle shown in Table 2, it carried out similarly to Example 1, and the black of Examples 2-4 and Examples 7, 8, and 12 A matrix was obtained.

Production of color filter

Fabrication of Photosensitive Resin Transfer Material

The photosensitive transfer material R, the photosensitive transfer material G, and the photosensitive transfer material B were produced using the coloring photosensitive resin composition of Table 1 below by the method similar to the said photosensitive transfer material K1 production.

Formation of red (R) pixel

The same process as the formation of the black matrix, except that the exposure phenomenon in the exposure step is 40 mJ / cm ² and the shower phenomenon with the Na carbonate developer is changed from 35 ° C. to 35 seconds and the heat treatment is changed from 220 ° C. to 15 minutes. The photosensitive resin transfer material R was used, and the red (R) pixel was formed in the side in which the black matrix of a glass substrate is formed.

The thickness of the R pixel and 2.0㎛, CI Pigment Red-(CIPR) 254, application amount of CIPR 177 are respectively ^{0.88g / m 2, 0.22g / m} 2.

Thereafter, the glass substrate on which the R pixel was formed was brush-washed again using a cleaning agent as described above, and after shower-cleaning with pure water, the silane coupling liquid was not used and the substrate preheating apparatus was used at 100 ° C. for 2 minutes. Heated.

Formation of Green (G) Pixels

The same process as the formation of the above R pixels except that the exposure amount in the exposure step is 40 mJ / cm ² , the shower phenomenon by Na carbonate developer is changed from 34 ° C. to 45 seconds, and the heat treatment is changed from 220 ° C. to 15 minutes. Using the photosensitive resin transfer material G obtained above, the green pixel (G pixel) was formed in the side in which the black matrix and R pixel of a glass substrate are formed.

The thickness of the G pixel is 2.0㎛, CI Pigment Green, (CIPG) 36, CI Pigment Yellow-(CIPY) coating amount of 150 each was ^{1.12g / m 2, 0.48g / m} 2.

Thereafter, the glass substrate on which the black matrix, the R pixel, and the G pixel was formed was brush-washed again using a cleaning agent as described above, and after shower-cleaning with pure water, the silane coupling liquid was not used, and the substrate preheater was used. Heated at 100 ° C. for 2 minutes.

Formation of Blue (B) Pixels

The photosensitive resin transfer material obtained by performing the same process as the above-mentioned R pixel formation except that the exposure amount in the exposure step was changed to 30 mJ / cm ² and the shower phenomenon by Na carbonate developer at 36 ° C. for 40 seconds. Using B, blue pixels (B pixels) were formed on the side where the black matrix of the glass substrate and the R pixels and the G pixels were formed.

The thickness of the B pixels and 2.0㎛, CI Pigment Blue, (CIPB) 15: 6, the application amount of CI Pigment Violet, (CIPV) 23 are respectively ^{0.63g / m 2, 0.07g / m} 2.

Then, the glass substrate in which each pixel of R, G, and B was formed was baked at 240 degreeC for 50 minutes, and the color filter was obtained.

The composition of the binder 2 in Table 1 is as follows.

27 parts of a polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 3.8 million)

Propylene glycol monomethyl ether acetate 73 parts

The composition of the DPHA liquid is as follows.

76 parts of dipentaerythritol hexaacrylate (containing a polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)

Propylene glycol monomethyl ether acetate 24 parts

 The composition of R pigment dispersion 1 is as follows.

C.I.P.R. 254 (brand name: Irgaphor Red B-CF, Chiba specialty chemicals production) eight copies

0.8 parts of Compound 1

8 parts of polymer (benzyl methacrylate / methacrylic acid = random copolymer of 73/27 molar ratio)

Propylene glycol monomethyl ether acetate 83 parts

Compound 1

The composition of R pigment dispersion 2 is as follows.

C.I.P.R. 177 (brand name: Cromophtal Red A2B, Chiba specialty chemicals production) 18 copies

Polymer (random copolymer of benzyl methacrylate / methacrylic acid = 73/27 molar ratio)

                                                           Part 12

70 parts of propylene glycol monomethyl ether acetate

The composition of the binder 1 is as follows.

27 parts of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, molecular weight 40,000)

Propylene glycol monomethyl ether acetate 73 parts

Additive 1 is a phosphate ester type special activator (brand name: HIPLAAD ED152, manufactured by Kutsumoto Chemical Co., Ltd.).

GT-2 (brand name, Fujifilm Electronics Co., Ltd. product) was used as G pigment dispersion 1.

As the Y pigment dispersion 1, CF yellow EX3393 (trade name, manufactured by Mikuni Shikiso Co., Ltd.) was used.

As the B pigment dispersion 1, CF blue EX3357 (trade name, manufactured by Mikuni Shikiso Co., Ltd.) was used.

As the B pigment dispersion 2, CF blue EX3383 (trade name, manufactured by Mikuni Shikiso Co., Ltd.) was used.

In addition, the composition of the binder 3 is as follows.

Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate

 (36/22/42 mole ratio random copolymer, molecular weight 3.8 million) 27 parts

Propylene glycol monomethyl ether acetate 73 parts

Examples 5 and 6

Formation of black matrix

The coating liquid for light shielding layers was apply | coated on a glass substrate by the same process as Example 1 except having prepared and used each coating liquid for light shielding layers to have a mixing ratio of the carbon black / silver particle shown in Table 2, The photosensitive light shielding layer used for Examples 5 and 6 was formed.

Subsequently, 500 mJ / cm <^2> pattern exposure was performed to the said photosensitive light shielding layer using the ultrahigh pressure mercury lamp. Then, a sodium carbonate developer containing 0.38 mol / liter of sodium bicarbonate, 0.47 mol / liter of sodium carbonate, 5% by mass of sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, and stabilizer as a developer. The photosensitive black resin layer of the light shielding layer was developed by using T-CD1, manufactured by Fujishashin Film Co., Ltd., diluted five times with pure water (29 ° C) to remove the unexposed portions, and the target Example 5 and A black matrix of 6 was formed. Thereafter, the color filters of Examples 5 and 6 were prepared in the same manner as in Example 1.

Example 9

The color filter shown in Table 3 was produced like Example 1 except having changed the "coating liquid for light shielding layers" used in Example 1 into the following "coating liquid for silver / silver sulfide containing light shielding layers."

Fabrication of silver / silver sulfide coreshell particles

0.95 g of vinylpyrrolidone / vinyl acetate copolymer (= 60/40 [mass ratio], molecular weight 5000) was added to 200 g of acetone dispersions (average particle diameter 30 nm, concentration 2.5 mass%) of silver particles, and it stirred for 30 minutes. Subsequently, while stirring the sodium sulfide aqueous solution (23 degreeC) of concentration 7.2 mass%, it adds so that the sulfidation rate of metal will be 30%, and after completion | finish of addition, stirring for 30 minutes as it is, and silver / silver sulfide which has a shell of silver sulfide Core shell particles were obtained.

Here, the sulfidation rate represents the ratio at which metal particles are sulfided. A sulfidation rate of 0% means a state that is not sulfided at all, and a sulfidation rate of 100% means a state in which the entire particle is completely sulfide.

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 the color filters shown in Table 3 were produced in the same manner as in Example 1.

Example 11

The color filter shown in Table 3 was produced like Example 1 except having changed the coating liquid for light shielding layers into the coating liquid for silver tin alloy containing light shielding layers below.

Preparation of AgSn Alloy Particle Dispersion (Dispersion A1)

In 1000 ml of pure water, 23.1 g of silver acetate (I), 65.1 g of tin (II) acetate, 54 g of gluconate, 45 g of sodium pyrrolate, 2 g of polyethylene glycol (molecular weight 3,000), and E735 (manufactured by ISP; vinylpyrrolidone / vinyl acetate) 5 g of copolymer) was 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.

The solution 2 was added to this over 2 minutes, stirring vigorously, maintaining solution 1 obtained at 25 degreeC, and stirring the mixed liquid obtained by the said addition was continued for 6 hours gently. Then, the mixed solution turned black, and silver tin (AgSn) alloy fine particles were obtained. Subsequently, the mixed solution was centrifuged to precipitate the AgSn alloy fine particles. In the centrifugation step, the mixed solution was subdivided into 150 ml portions each, and a 30-minute centrifugal separator (trade name: H-103n, manufactured by Kokusan Co., Ltd.) was used for 30 minutes at a speed of 2,000 r.p.m. After the centrifugation, the supernatant in the sample was discarded to make the total liquid amount 150 ml. 1350 ml of pure water was added to the sample, followed by stirring for 15 minutes to disperse the AgSn alloy fine particles again. This precipitation and dispersion operation was repeated twice to remove the soluble material in the aqueous phase.

Thereafter, centrifugation was further performed, and the AgSn alloy fine particles were precipitated again. Centrifugation was performed on the same conditions as the above. After centrifugation, the supernatant was discarded in the same manner as described above to make the total liquid amount to 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 further disperse the AgSn alloy fine particles.

In the same manner as above, centrifugation was carried out to precipitate AgSn alloy fine particles, and then the supernatant was discarded as described above to make 150 ml of liquid, and 150 ml of pure water and 1200 ml of acetone were added thereto, followed by further stirring for 15 minutes. Was dispersed again. And again, centrifugation was performed. The conditions for centrifugation at this time were the same as above except that the time was extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid amount 70 ml, and 30 ml of acetone was added thereto. This was disperse | distributed for 6 hours using the Eiger mill (brand name: M-50 form (medium: 0.65 mm diameter zirconia beads), Eiger Japan make), and obtained the silver tin (AgSn) alloy fine particle dispersion. As a result of observing this fine particle dispersion with a transmission electron microscope, the dispersion average particle diameter was about 40 nm in number average particle size.

Preparation of coating liquid for silver tin alloy containing light shielding layer

The following composition was mixed and the coating liquid for silver tin alloy containing light shielding layers was prepared.

50.00 parts of the above-described AgSn alloy particle dispersion (dispersion A1)

Propylene glycol monomethyl ether acetate 28.6 parts

Methyl ethyl ketone 37.6 parts

0.2 part of the fluorine-based surfactant

0.001 part of hydroquinone monomethyl ether

Styrene / acrylic acid copolymer (molar ratio = 56/44, weight average molecular weight 30,000)

                                                             Part 9.6

Dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 9.6

0.5 parts of bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate

Comparative Examples 1 to 4

In the same manner as in Example 1, the addition amount of carbon black, silver particles, and the like were adjusted to prepare a color filter shown in Table 3.

In the obtained color filters, the TFT-side reflectance, the transmission optical density, the transmission optical density per unit film thickness, the film thicknesses of R, G, and B, the film thickness ratios (TR / BM, TG / BM and TB / BM), the projection height, Chromaticity and display nonuniformity are measured, and the result is shown to Table 2 and Table 3.

Fabrication of Liquid Crystal Display

On the R pixels, G pixels, and B and black matrices of each color filter substrate obtained in the above Examples and Comparative Examples, transparent electrodes of ITO (Indimum Tin Oxide) were formed by sputtering. Subsequently, according to Example 1 of JP-A-2006-64921, a spacer was formed in a portion corresponding to the upper part of the partition (black matrix) on the ITO film formed 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 the alignment film which consists of polyimide was further formed on it.

Then, the sealing compound of ultraviolet curable resin was apply | coated by the dispenser method at the position corresponded to the black matrix outline formed around the pixel group of a color filter by the dispenser method, the liquid crystal for PVA mode was dripped, and it bonded together with the counterpart substrate. . The bonded substrate was irradiated with UV and then heat treated to cure the sealing agent. The polarizing plate (brand name: HLC2-2518, the Sanlitz Corporation make) was attached to both surfaces of the liquid crystal cell obtained in this way. Subsequently, FR1112H (brand name, manufactured by Stanley Co., Ltd.) which is a chip type LED as a red (R) LED, and DG1112H (brand name, manufactured by Stanley Co., Ltd.), which is a chip type LED as a green (G) LED, and a blue (B) LED. The backlight of the side light system was comprised using DB1112H (brand name, Stanley Co., Ltd.) which is a chip | tip LED. The said backlight was arrange | positioned at the side used as the back surface of the liquid crystal cell in which the said polarizing plate was formed, and the liquid crystal display device was created.

Assessment Methods

Film thickness measurement

The film thickness was measured about each black matrix or colored pixel formed after baking using the contact surface roughness meter (brand name: P-10, the product made by TENCOR Corporation).

Transmission optical density measurement

The transmission optical density of the black matrix was measured by the following method.

First, exposure of 500 mJ / cm ² from the application surface side using the material having the black matrix formed in the Examples and Comparative Examples and using the ultra-high pressure mercury lamp on the light shielding layer coated with a thin film so that the OD is 3.0 or less on the glass substrate Was performed. Next, this optical density (OD) was measured using the Macbeth densitometer (brand name: TD-904, Macbeth company make). Separately, the transmission optical concentration (OD ₀ ) of the glass substrate was measured by the same method. Using a contact surface roughness meter (trade name: P-10, manufactured by KLA Tencor Co., Ltd.), the film thickness of the sample for measurement was measured, and the value obtained by subtracting OD ₀ from the OD was obtained by transmitting optical concentration of the light shielding layer. The optical density of the black matrix of the film thickness produced in the Example was computed from the relationship between the transmission optical density and the film thickness of the said measurement result.

TFT side reflectance measurement

Absolute reflectance measuring device (trade name: ARV-474, manufactured by JASCO Corporation) in combination with a spectrophotometer (trade name: V-560, manufactured by JASCO Corporation), and the absolute side of the TFT-side reflectance (the surface on which the coating film is formed) Reflectance was measured.

The measurement angle is 5 degrees from the vertical direction and the wavelength is 555 nm.

Particle diameter measurement

100 particle | grains are measured by a transmission electron microscope (brand name: JEM-2010, magnification 200000 times, Japan Electronics (made by JEOL Ltd.), and converted into the circle of a projection area coplanar area, and let the diameter be a particle diameter, The average value was made into that value.

Measurement of chromaticity

The chromaticity of the color filter obtained above was measured with the pinhole diameter of 5 micrometers using the brown rice spectrophotometer (brand name: OSP100, Olympus Kogakusha Co., Ltd.), and computed it as a result of C light source visual field 2 degree | times.

Display mixed color

In an Example and a comparative example, red (R), green (G), and blue (B) were simultaneously developed, and the density nonuniformity in the range of a fixed area (10 cm x 10 cm) was visually determined. The determination was carried out by ten people, and the evaluation was made by A when the number of people determined to have a concentration unevenness was zero, B when the number of people was 1 to 2, and X when the number of people was 3 or more.

TFT malfunction

A part of the backlight of the LCD reflects on the surface of the black matrix layer, becomes incident light to the TFT, and becomes leaked light in black display. The presence of this leaked light was evaluated as a malfunction. Its presence or absence is shown in Table 2 and Table 3. About leakage light, it evaluated by confirming in the dark.

Non-uniform indication

When the gray test signal was input to the liquid crystal display device, it was observed with the naked eye and a loupe, and the presence or absence of the generation of the nonuniformity was judged.

LR *: Developing method by using liquid resist

From the result of Table 2 and Table 3, the following is confirmed.

Even if the thickness of the black matrix is reduced, the color filter of the embodiment has a high transmission optical density, a high transmission optical density per unit film thickness, and a good chromaticity so that there is no display unevenness and the TFT-side reflectance is low, thereby providing excellent contrast. .

The color filter and liquid crystal display device for a liquid crystal display device of the present invention are excellent in display contrast in bright room, have no malfunction of TFTs, are not uneven in display, 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 formed on the transparent substrate: A colored pixel of green color (G) in a region partitioned by the black matrix; A part of the colored layer of said G (green) colored pixel is laminated on a part of said black matrix; The black matrix contains a pigment and at least one selected from metal particles and metal compound particles; The ratio (B / A) of the content B of the pigment to the content A of the metal particles and the metal compound particles in the black matrix is in the range of 0.2 to 10; Also The film thickness ratio (TG / BM) of the film thickness TG of said G (green) colored pixel and the film thickness BM of a black matrix is in the range of 1.2-10, The color filter for liquid crystal display devices characterized by the above-mentioned. The method according to claim 1, further comprising colored pixels of R (red) and colored pixels of B (blue) in a region defined by the black matrix; The film thickness TR of the colored pixel of R (red) and the film thickness ratio TR / BM of the BM are in the range of 1.2 to 10; Also The film thickness TB of the colored pixel of said B (blue) and the film thickness ratio (TB / BM) of said BM exist in the range of 1.2-10, The color filter for liquid crystal display devices characterized by the above-mentioned. The liquid crystal display device according to claim 1 or 2, wherein the height of the projections relative to the colored pixels of the projections formed by laminating a part of the colored layers of the colored pixels on a part of the black matrix is 0.4 µm or less. Color filter. The color filter for a liquid crystal display device according to any one of claims 1 to 3, 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 according to the C light source of G (green) is in the chromaticity range of G (x≤0.32, y≥0.56). Color filter for liquid crystal display device. The chromaticity point according to any one of claims 2 to 5, wherein the chromaticity point on the CIE chromaticity diagram of three primary colors of R (red), G (green), and B (blue) is R (x≥0.62, A color filter for a liquid crystal display device, characterized by being in a chromaticity range of y ≦ 0.35), G (x ≦ 0.32, y ≧ 0.56) and B (x ≦ 0.17, y ≦ 0.14). The color filter according to any one of claims 1 to 6, 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 or metal compound particles contained in the black matrix are metal particles. The color for a liquid crystal display device according to any one of claims 1 to 7, wherein the metal particles or metal compound particles contained in the black matrix contain at least one selected from Ag fine particles and AgSn alloy fine particles. filter. The liquid crystal display device according to any one of claims 1 to 9, wherein the black matrix comprises a photosensitive resin composition containing the pigment and at least one selected from the metal particles and the metal compound particles. Color filter. The liquid crystal display device according to claim 1, wherein the black matrix comprises a photosensitive transfer material containing the pigment and at least one selected from the metal particles and the metal compound particles. Color filter. The liquid crystal display device containing the color filter for liquid crystal display devices of any one of Claims 1-11.

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