CN100588994C - 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 themetal 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.

Description

Color filter and use the liquid crystal indicator of this color filter

Technical field

The present invention relates to a kind of liquid crystal display device color filter and liquid crystal indicator, relate in particular to and show that contrast is outstanding, do not have the misoperation of TFT, show uneven and can realize the liquid crystal display device color filter and the liquid crystal indicator of high color purity and high permeability simultaneously.

Background technology

The color filter that uses in the colour liquid crystal display device etc. forms colored pixels (R, G, B) on transparency carrier, and shows contrast etc. in order to improve, and forms black matrix in the gap of R (redness), G (green), each colored pixels of B (blueness).Except above-mentioned purpose, the reduction of picture quality also takes place in order to prevent thin film transistor (TFT) from causing the electric current leakage under light action thereupon, and especially the black matrix that need use in the liquid crystal display cells of the driven with active matrix mode of using thin film transistor (TFT) (TFT) has high light-proofness.

Metal films such as chromium are comprised following method as the known example of the formation method of the black matrix of light shield layer: utilize vapour deposition method or sputtering method to make metallic film, on this metallic film, apply photoresist, then via photomask with pattern that black matrix uses, exposure, development photoresist layer, the metallic film that exposes of etching then, resist layer on the last stripping metal film (for example " colored TFT LCD " the 218th～220 page (upright altogether publish (strain), distribution on April 10th, 1997)).

This method is owing to using metallic film, so even thickness is thin, also can obtain high shaded effect.On the contrary, the vacuum film formation operation or the etching work procedure of essential vapour deposition method or sputtering method and so on, cost uprises but also has the very important burden problem to environment.In addition, this method is owing to be metal film, and reflectivity rises, and also has the problem that causes that the misoperation of TFT or the contrast in the room reduce.At these problems, proposed to use the mechanism of low reflective chrome film (by 2 layers of film that constitutes of crome metal and chromium oxide etc.), but undeniable, utilize this mechanism, cost can be higher.

In addition, the also known method that has use to contain the photosensitive polymer combination of light-proofness pigment (for example carbon black) of other known examples of the formation method of black matrix.The black matrix formation method of so-called autoregistration (selfalignment) mode is included in after each pixel that forms R, G, B on the transparency carrier, coating contains the carbon black photosensitive polymer combination on this pixel, the operation (for example the spy opens clear 62-9301 number) of exposing all sidedly from the non-formation face side of R, G, B pixel of this transparency carrier.

This method is compared with the etching method that utilizes described metal film, although low cost of manufacture must thickness be about 1.1～1.4 μ m in order to obtain sufficient light-proofness (for example OD=4.0).The result that this thickness increases overlaps (difference of height) between each pixel of deceiving matrix and R, G, B, the flatness variation of color filter, and the unit interval of liquid crystal display cells takes place uneven, thereby causes that look unequal demonstration is bad.

Therefore, thus in order to make the thickness attenuation obtain the high film of OD, proposed to use the photosensitive polymer combination that contains metallics to make the technology (spy opens 2004-240039 number) that black matrix is made the photomask of usefulness.

And then, for the tone that makes black matrix near black, also proposed to have the black matrix (spy opens 2004-317897 number) of the photomask of containing metal particle and pigment particle.

But if the content of the metallics in the black matrix is many, then metallic luster can cause that reflectivity rises, so using when should black matrix making color filter the problem that exists the room contrast to reduce.In addition, if the content of the black pigment particulate in the black matrix is many, then the thin layerization of black matrix is difficult to, the thickness thickening of black matrix.As a result, black matrix and R, G, B (red, green, blue) pixel overlap (difference of height), the flatness variation of color filter, and the unit interval of liquid crystal display cells takes place uneven, thereby causes that look unequal demonstration is bad.

Non-patent literature 1: " colored TFT LCD " the 218th～220 page (upright publication (strain) altogether, distribution on April 10th, 1997)

Patent documentation 1: the spy opens clear 62-9301 communique

Patent documentation 2: the spy opens the 2004-240039 communique

Patent documentation 3: the spy opens the 2004-317897 communique

Summary of the invention

The present invention In view of the foregoing forms.The invention provides a kind of demonstration contrast in the room outstanding, do not have the misoperation of TFT, show uneven and can realize the liquid crystal display device color filter and the liquid crystal indicator of high color purity and high permeability simultaneously.

Above-mentioned purpose of the present invention can realize by liquid crystal display device color filter, liquid crystal indicator that following structure is provided.

(1) a kind of liquid crystal display device color filter, it is the liquid crystal display device color filter that contains transparency carrier and be arranged at the black matrix on this transparency carrier, it is characterized in that:

G (green) colored pixels is contained in zone in the separation of this black matrix;

The part of the dyed layer of stacked this G of a part (green) colored pixels on this black short battle array;

Should black matrix contain pigment and from metallics and metallic compound particle, select at least a;

The content B of the pigment in this black matrix relatively the ratio (B/A) of the content A of this metallics and metallic compound particle in 0.2～10 scope; And

The Film Thickness Ratio (TG/BM) of the thickness TG of this G (green) colored pixels and the thickness BM of black matrix is in 1.2～10 scope.

(2) according to the liquid crystal display device color filter of record in described (1), it is characterized in that,

In zone that this black matrix is separated and then contain R (redness) colored pixels and B (blueness) colored pixels;

The thickness TR of this R (redness) colored pixels and the Film Thickness Ratio (TR/BM) of described BM are in 1.2～10 scope; And

The thickness TB of this B (blueness) colored pixels and the Film Thickness Ratio (TB/BM) of described BM are in 1.2～10 scope.

(3) according to the liquid crystal display device color filter of record in described (1) or (2), it is characterized in that,

The jut that the part of the dyed layer of the stacked colored pixels of a part on described black matrix forms is color pixel and the height of projection is below the 0.4 μ m vis-a-vis.

(4) according to the liquid crystal display device color filter of record in described (1)～(3) any, it is characterized in that,

The penetrating concentration of described black matrix is more than 3.5 and thickness is below the 1.3 μ m.

(5) according to the liquid crystal display device color filter of record in described (1)～(4) any, it is characterized in that,

Chroma point on the XYZ chromaticity diagram of utilizing illuminant-C of the G of described record (green) is in the chromaticity range of G (x≤0.32, y 〉=0.56).

(6) according to the liquid crystal display device color filter of record in described (2)～(5) any, it is characterized in that,

Chroma point on the XYZ chromaticity diagram of the illuminant-C that utilizes 3 primary colors of the R of described record (redness), G (green), B (blueness) is in the chromaticity range of R (x 〉=0.62, y≤0.35), G (x≤0.32, y 〉=0.56) and B (x≤0.17, y≤0.14).

(7) according to the liquid crystal display device color filter of record in described (1)～(6) any, it is characterized in that,

Described pigment contains select at least a from carbon black and graphite.

(8) according to the liquid crystal display device color filter of record in described (1)～(7) any, it is characterized in that,

Metallics that contains in the described black matrix or metallic compound particle are metallics.

(9) according to the liquid crystal display device color filter of record in described (1)～(7) any, it is characterized in that,

Metallics that contains in the described black matrix or metallic compound particle contain select at least a from Ag particulate and AgSn alloy particle.

(10) according to the liquid crystal display device color filter of record in described (1)～(9) any, it is characterized in that,

Described black matrix contains: at least a photosensitive polymer combination that contains described pigment and select from described metallics and metallic compound particle.

(11) according to the liquid crystal display device color filter of record in described (1)～(10) any, it is characterized in that,

At least a photosensitive transfer printing material that described black matrix contains described pigment and selects from described metallics and metallic compound particle.

(12) a kind of liquid crystal indicator is characterized in that,

The liquid crystal display device color filter that contains record among any in described (1)～(11).

Utilize liquid crystal display device color filter of the present invention and liquid crystal indicator, at the demonstration contrast height in room, do not have the misoperation of TFT, show uneven and can realize high color purity and high permeability simultaneously.

Description of drawings

Fig. 1 is the synoptic diagram of an embodiment of the height of the thickness of the colored pixels of expression in the comparative example and jut.

Fig. 2 is the synoptic diagram of another embodiment of the height of the thickness of the colored pixels of expression among the present invention and jut.

Embodiment

Liquid crystal display device color filter of the present invention has black matrix on transparency carrier.Separated region at this black matrix has G (green) colored pixels at least.The part of the dyed layer of stacked this G of the part on this black matrix (green) colored pixels.This black matrix contains pigment and metallics and/or metallic compound particle and forms.The ratio (mass ratio) of the content A of this metallics and/or metallic compound particle and the content B of pigment is more than 0.2 below 10 (B/A).In addition, the ratio (Film Thickness Ratio) of the thickness TG of this G (green) colored pixels and the thickness BM of black matrix is more than 1.2 below 10 (TG/BM).

Below the main composition important document of liquid crystal display device color filter of the present invention is elaborated.Wherein, the present invention is not limited by these explanation items.

In the present invention, contain at least a of pigment and metallics and metallic compound particle at least in the black matrix.They contain in black matrix with the state that disperses in macromolecular compound at least.

The metallics that uses in the present invention is not particularly limited, can uses any one.The example of the preferable alloy that this metallics contains as its principal ingredient comprises the metal of selecting in the family that the metal selected in the group that the 4th cycle, the 5th cycle and the 6th cycle of the periodic table of elements constitute and the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family and the 14th family constitute.In these metals, more preferably be in the 4th cycle, the 5th cycle or the 6th cycle and be in the metal of the 10th family, the 11st family or the 12nd family, and then preferred gold, silver, copper, platinum or palladium.Wherein, especially preferred silver.The silver that contains in the metallics of the present invention most preferably is collargol.The manufacturing of metallics also can be made up two or more above-mentioned metals.In addition, the manufacturing of metallics also can be used the alloy that two or more above-mentioned metals constitute.

Metallics can use commercially available metallics.In addition, metallics can also utilize the chemical reduction method of metallic ion, electroless plating to apply preparations such as method, evaporation of metals method.

The example of preparing the method for silver-colored particulate (collargol) comprises United States Patent (USP) the 2nd, 688, the disclosed quinhydrones that utilizes reduces the method for soluble silver salt in No. 601 instructionss in aqueous gelatin solution, at Deutsche Bundespatent the 1st, 096, the method of putting down in writing in No. 193 instructionss of utilizing hydrazine reduction slightly solubility silver salt, United States Patent (USP) the 2nd, 921, the tannic acid of putting down in writing in No. 914 instructionss that utilizes is reduced into the method for electronation silver ion in solution of method and so on of silver, the electroless plating of putting down in writing in the Te Kaiping 5-134358 communique that utilizes apply to form the method for silver particles, makes the bulk metal evaporation and then known in the past methods such as method such as evaporation method take place in solvent in the gas of cold trap (cold trap) in inert gases such as helium.In addition, the example of preparing the method for silver-colored particulate (collargol) also comprises Wiley﹠amp; Sons, NewYork, the compound method of the yellow colloidal silver of the dextrin reducing process of utilizing Carey Le of record in " colloid element (the Colloidal Elements) " of distribution in 1933, Weiser work.

Described in the present invention " metallic compound " is meant the compound of the element beyond above-mentioned metal and the metal.The example of the compound of metal and other metals comprises oxide, sulfide, sulfate, carbonate of metal etc.From the easy degree of tone or formation particulate, preferred especially these sulfide.The example of these metallic compounds comprises that cupric oxide (II), iron sulfide, silver sulfide, copper sulfide (II), titanium are black etc.Wherein, from tone, the easy degree that forms particulate and stable viewpoint, preferred especially silver sulfide.

Metallic compound particle described in the present invention also comprises example as described below.

(1) particulate of above-mentioned metallic compound formation

(2) the two or more metallic compound particles particulate of 1 particle that is composited

(3) particulate that constitutes by metallics and metallic compound particle

The concrete example of the particulate that two or more metallic compound particles are composited comprises the composite particles of silver and composite particles, copper sulfide and the silver sulfide of silver sulfide, the composite particles of silver-colored and cupric oxide (II) etc.

In addition, the concrete example of the particulate that is made of metallics and metallic compound particle comprises the composite particles of silver and composite particles, copper sulfide and the silver sulfide of silver sulfide, the composite particles of silver-colored and cupric oxide (II) etc.

Shape to composite particles is not particularly limited.The example of this shape comprises shape that the inside of the particle shape different with surface composition, two kinds of particles integrate etc.

The metallics of use in the present invention and/or the particle diameter of metallic compound particle are not particularly limited.This mean grain size is preferably in the scope of 10～3000nm, and more preferably mean grain size is in the scope of 30～2000nm, and then in the preferred scope about 60～200nm.Wherein, under the situation for the metallic compound particle (not being composite particles) of above-mentioned (1), if mean grain size less than 60nm, then tone sometimes variation some.In addition, when particle diameter surpasses 300nm,, not preferred sometimes from the point of dispersiveness.

Size distribution to metallics and/or metallic compound particle is not particularly limited.

In order to obtain necessary optical concentration, metallics of Shi Yonging and/or metallic compound particle must be for coloured in the present invention.At this, colouredly be meant that the wavelength region may at 400～700nm has optical absorption.The example of non-ferrous metal compound comprises that silver sulfide, copper sulfide, iron sulfide, palladium sulfide, silver oxide, titanium are black etc.

Shape to metallics of the present invention and/or metallic compound particle is not particularly limited.The example of operable this shape of particle comprises sphere, unsetting, tabular, cube, regular octahedron, column etc.

As required, also can mix and use composition, shape, particle diameter, two or more metallicss and/or metallic compound particle that the optical absorption wavelength region may is different.

In addition, for the manufacture method of metallics, for example be recorded in " the up-to-date trend II of ultramicronized technology and application (living ペ テ Network ノ リ サ one チ (strain) distribution, 2002) ".

Pigment

In the present invention, as pigment, especially can preferably use the black pigment particulate.This example comprises pigment black 7 (carbon black C.I.No.77266, trade name: the carbon black MA100 of Mitsubishi (Mitsubishi Chemical's (strain) system) for example, trade name: the carbon black #5 of Mitsubishi (Mitsubishi Chemical's (strain) system), trade name: Black Pearls 430 (Cabot Co. (キ ヤ ボ Star ト company) system), graphite etc.Wherein, preferred especially carbon black and graphite.

The metallics among the present invention and the mean grain size of pigment particle are under the observation that utilizes transmission electron microscope (TEM), measure 50 particle diameters, and then calculate the value of its mean value gained.

Constitute the scope of ratio (mass ratio B/A) of the amount B of the amount A of the metallics that contains in the black matrix of color filter of the present invention and/or metallic compound particle and pigment, preferably in 0.3～6.0 scope, more preferably in 0.8～5.0 scope 0.2～10.Described mass ratio B/A less than 0.2 situation under because the addition of metallics in the black matrix and/or metallic compound particle is many, so the reflectivity of black matrix uprises, so become the misoperation of TFT takes place easily.On the other hand, surpass under 10 the situation at described mass ratio B/A, because metallics and/or metallic compound particle in the black matrix are few, reduce so deceive the optical concentration that sees through of matrix, sometimes the thickness of the black matrix of essential raising in order to keep the seeing through optical concentration of regulation.As a result, overlap (difference of height) between black matrix and R, G, each pixel of B, thus the flatness variation of color filter, generating unit spacing inequality in the liquid crystal display cells.This inequality causes easily that in liquid crystal indicator of the present invention look unequal demonstration is bad.

In addition, the Film Thickness Ratio (TG/BM) of the thickness (TG) of G (green) colored pixels that visibility is the highest in constituting the rgb pixel of color filter of the present invention and the thickness (BM) of black matrix is in 1.2～10 scope, preferably in 1.4～5.0 scope, more preferably in 2.0～4.0 scope.In addition, Film Thickness Ratio TR/BM, the TG/BM of the thickness BM of each thickness TR, TG, TB and the black matrix of R (redness), G (green), B (blueness) colored pixels and TB/BM are all preferably in 1.2～10 scope, more preferably these Film Thickness Ratio are 1.4～5.0 scope, and then preferably these Film Thickness Ratio are 2.0～4.0 scope.

At this, the thickness of colored pixels is as described below.That is, in Fig. 1, the thickness of colored pixels is meant the thickness of the flat of colored pixels 10, is meant the thickness of representing with Ha.(in Fig. 1, BM＞Ha.) in addition, in Fig. 2, the thickness of colored pixels is meant the thickness of the flat of colored pixels 12, is meant the thickness of representing with Hc.(in Fig. 2, Hc＞BM.)

In the present invention, preferably in the part of the dyed layer of the stacked colored pixels of the last branch of described black matrix (G) and the jut that forms color pixel and the height of projection is preferably the scope of 0～0.4 μ m vis-a-vis, the scope of 0～0.3 μ m more preferably, and then be preferably the scope of 0～0.2 μ m.At this, the rising height of the jut on the black matrix is as described below.That is, in Fig. 1, rising height is meant from the height (thickness) of the part of the thickness projection of the flat of deceiving the colored pixels 10 on the matrix (BM), is meant the thickness Hb of jut.In addition, in Fig. 2, rising height is meant the height (thickness) from the part of the thickness projection of the flat of colored pixels 12, is meant the thickness Hd of jut.If the height (thickness) of the jut of the colored pixels on the black matrix is greater than 0.4 μ m, then the disorder of the liquid crystal aligning that causes of the thickness difference of the pixel passed through of light may cause and produces the look inequality, so not preferred.

The penetrating concentration of preferred black matrix is in 3.5～10.0 scope and the thickness scope at 0.1～1.3 μ m.More preferably this penetrating concentration more than 3.8 and also this thickness below 1.1 μ m.And then preferably this penetrating concentration more than 4.0 and also this thickness below 1.0 μ m.If the penetrating concentration of black matrix is high and this thickness is enough thin in the scope that can guarantee sufficient shading, then be difficult to produce overlapping (difference of height) of black matrix and R, G, each pixel of B, so can improve the flatness of color filter.So, be difficult to produce inequality, so it is bad to be difficult to take place look unequal demonstration at the unit interval of liquid crystal display cells.

The example that is used for deceiving the penetrating concentration of matrix and the mechanism of film thickness monitoring in above-mentioned scope comprises the pigment of black matrix and the mass ratio of metallics and/or metallic compound particle etc. adjustment is waited within the limits prescribed.

Black matrix

Black matrix of the present invention is preferably by containing pigment and metallics and/or metallic compound particle and then containing the polymkeric substance that becomes bonding agent or the resin combination of dispersion stabilizer and surfactant etc. forms.Above-mentioned black matrix especially preferably utilizes and has the photosensitive photosensitive polymer combination that contains metallics (below be also referred to as " black matrix is made and use composition ") formation.The example that is used for giving so photosensitive this photosensitive polymer combination comprises that the spy opens paragraph numbering [0016]～[0022] of flat 10-160926 communique and the composition that [0029] is put down in writing.

Use in the mode of water dispersion under the situation of metallics at silver colloid as described, it is the composition that aqueous medium is that preferred described black matrix is made with composition.The example that the black matrix of such water system is made of composition comprises that the spy opens the composition of record in the paragraph of flat 8-271727 communique [0015]～[0023], and the preference of commercially available said composition comprises SPP-M20 (trade name, Japan changes into industry (strain) system) etc.

Black matrix is made and also can be added optical polymerism compound or Photoepolymerizationinitiater initiater and inhibitor with composition and wait and prepare.

Described black matrix make preference with the optical polymerism compound that uses in the composition comprise have the ethene unsaturated double-bond, can be under the irradiation of light the monomer or the oligomer of addition polymerization.As the such monomer and the example of oligomer, be included in have in the molecule at least 1 can addition polymerization ethene unsaturated group, boiling point be the compound more than 100 ℃ under normal pressure.

As the object lesson of this optical polymerism compound, can enumerate to monofunctional acrylate or simple function methacrylates such as polyglycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate and (methyl) acrylic acid phenoxy group ethyl esters; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate; The polyfunctional acrylic ester or the multifunctional methacrylates such as product of (methyl) acroleic acid esterification after polyfunctional alcohol's addition of ethylene oxide of trimethylolpropane or glycerine etc. or epoxypropane.

The concrete example of this optical polymerism compound and then comprise special public clear 48-41708 communique, special public clear 50-6034 communique and the special urethane acrylate class of putting down in writing in the clear 51-37193 communique of opening; The spy opens the polyester acrylate class of putting down in writing in clear 48-64183 communique, special public clear 49-43191 communique and the special public clear 52-30490 communique; The polyfunctional acrylic ester or the methacrylates such as epoxy acrylate class of epoxy resin and (methyl) acrylic acid resultant of reaction.Wherein, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc.

It is two or more that these monomers or oligomer can be used alone or mix use.The content that the described relatively black matrix of this optical polymerism compound is made of all solids composition of composition is generally 5～50 quality %, is preferably 10～40 quality %.

The example that black matrix of the present invention is made of the Photoepolymerizationinitiater initiater that using in the composition comprises disclosed many promises of vicinal polyketals base (De ニ Le) compound in No. 2367660 instructions of United States Patent (USP), the accidental cause ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series accidental cause compound of putting down in writing in No. 2722512 instructions of United States Patent (USP) with α-hydrocarbon replacement, the polynucleation quinone compound of putting down in writing in No. 3046127 instructions of United States Patent (USP) and No. 2951758 instructions of United States Patent (USP), the triarylimidazoles dimer of putting down in writing in No. 3549367 instructions of United States Patent (USP) with to the combination of amino ketones, benzothiazole compound and the trihalomethyl group-s-triaizine compounds put down in writing in the special public clear 51-48516 communique, the trihalomethyl group triaizine compounds of putting down in writing in No. 4239850 instructions of United States Patent (USP), the San Lu that puts down in writing in No. 4212976 instructions of United States Patent (USP) is for Jia oxadiazole compound etc.Preferred especially trihalomethyl group-s-triazine, San Lu are for Jia oxadiazole and triarylimidazoles dimer.The black relatively matrix of described Photoepolymerizationinitiater initiater is made the content with all solids composition of composition, is generally 0.5～20 quality %, is preferably 1～15 quality % especially.

Black matrix among the present invention is made and can further be contained inhibitor (thermal polymerization inhibitor) with composition.The example of this thermal polymerization inhibitor comprises quinhydrones, p methoxy phenol, two-tert-butyl group-to pyrogallol, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, phenothiazine etc.

As required, also can make of containing various adjuvants in the composition by black matrix in the present invention, for example plastifier, surfactant, adhesion promoter, ultraviolet light absorber, solvent etc.

Black matrix making among the present invention is used to prepare become with composition above-mentioned each solid constituent is dissolved or dispersed in the coating liquid that forms in the solvent, with its coating on the surface of substrate or interim supporter etc., drying, forms the pigmentary resin layer.

Comprise methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid esters, cyclohexanone, cyclohexanol, ethyl lactate, methyl lactate, caprolactam etc. being used for preparing the described representative examples of organic that black matrix makes of composition.

Black matrix with the thickness of resin bed (below be also referred to as " light shield layer ") by finally deciding at the structure of the distance piece portion that forms on the color filter and unit interval and at the slip etc. that the black matrix that uses black matrix making with composition forms the thickness in the operation.

Black matrix making usefulness composition among the present invention can apply on the surface of substrate or interim supporter described later with known method, drying, thereby forms photonasty sheet material (light shield layer).

The example that black matrix is made of the applying mechanism of composition comprises slit coating machine, spinner, universal stage (whirler), roll coater, curtain formula coating machine, scraper plate coating machine, wire bar coating machine, extruder etc.This established overlay can by after dry photo-sensitive resin or the photosensitive transfer printing sheet material of obtaining.

Photosensitive transfer printing material

In the present invention, can use above-mentioned have photosensitive black matrix and make with pigment and metallics and/or metallic compound particle and contain composition, make photosensitive transfer printing material, use this photosensitive transfer printing material to make black matrix.This photosensitive transfer printing material is to be provided with to have above-mentioned photonasty at least and contain pigment and the black matrix of metallics and/or metallic compound particle makes the member of the photonasty light shield layer that constitutes with composition on interim supporter.The thickness of this photonasty light shield layer is preferably the scope about 0.3～3.0 μ m, more preferably the scope about 0.5～2.0 μ m.

Above-mentioned photosensitive transfer printing material contains composition as this photoresist material except using above-mentioned photonasty pigment and metallics and/or metallic compound particle, can have the structure substantially the same with known photosensitive transfer printing material.The example of structure of known photosensitive transfer printing material is recorded in the spy and opens flat 5-173320 communique etc.The basic structure of such photosensitive transfer printing material comprises that the sheet material of the interim supporter that is made of the plastic sheeting of softness etc. and the black matrix that forms make the thin layer that constitutes with composition on this interim supporter.The undercoat or the middle layer of layer of the buffering that the layer peeled off easily between them can at random be set, becomes light shield layer between interim supporter and light shield layer etc. and so on.The preferred construction example is included in the structure that is formed with alkali soluble thermoplastic resin bed, middle layer on the interim supporter, also has light shield layer.Also can be on light shield layer and then stacked guard film easily.

As above-mentioned interim supporter, middle layer, the thermoplastic resin among the present invention, can use and special identical interim supporter, middle layer, the thermoplastic resin of putting down in writing in paragraph numbering [0034]～[0040] of 2004-347801 communique of opening.

The operation of making photosensitive transfer printing material of the present invention can comprise uses for example applying mechanisms such as slit coating machine, spinner, universal stage (whirler), roll coater, curtain formula coating machine, scraper plate coating machine, wire bar coating machine, extruder, and coating on interim supporter, the dry black matrix that has photonasty and contain metallics of the present invention make the solution with composition.Be provided with above-mentioned alkali-soluble thermoplastic resin the layer situation under, also can make this alkali-soluble thermoplastic resin with identical operation.

As mentioned above, photosensitive transfer printing material of the present invention contains the photonasty light shield layer that composition constitutes in order to be provided with pigment and metallics and/or metallic compound particle, can use this transfer materials, be provided as the high light shield layer of film and optical concentration and make black matrix.

The making of black matrix

Black matrix of the present invention forms by using above-mentioned (photonasty) pigment particles and metallics and/or metallic compound particle to contain composition or having the light shield layer that the photosensitive transfer printing material of said composition makes.The thickness that should deceive matrix is generally about 0.1～1.3 μ m.Black matrix of the present invention is owing to disperseing pigment particles and metallics and metallic compound particle equably, so even for having the film of the thickness in the above-mentioned scope, also can demonstrate sufficient optical concentration (shielding properties).

Use has photosensitive pigment particles and metallics and/or metallic compound particle and contains composition and make the example of the method for black matrix and comprise and utilize conventional method, there are photosensitive metallics and/or metallic compound particle to contain on the layer (light shield layer) of composition formation at coating tool on the substrate of photopermeability, the photomask of using via black matrix exposes, and passes through the method for the black matrix of development formation etc. then.Coating method when this plating particle and/or metallic compound particle contain the described photosensitive transfer printing material of method for compositions use similarly.

In addition, containing composition at pigment particles and metallics and/or metallic compound particle does not have under the photosensitive situation, can contain on the layer of composition formation at coating pigment particles and metallics and/or metallic compound particle on the photopermeability substrate, the layer that formation is made of the photosensitive polymer combination that can develop, utilize conventional method, expose with photomask via black matrix, then development, etching form black matrix.

Use the method for making of the black matrix of described photosensitive transfer printing material can utilize mode with the photonasty light shield layer contact of photosensitive transfer printing material, preparation, stacked this photosensitive transfer printing material on the photopermeability substrate, then, from peeling off interim supporter by the duplexer of photosensitive transfer printing material and photopermeability substrate, after this photonasty light shield layer being exposed with photomask via black matrix then, develop, thus the method for the black matrix of formation etc.Like this, the manufacture method of black matrix of the present invention do not need loaded down with trivial details operation and also easy, cost is low.

Coloured composition and pigment

Then, the composition that the colored pixels of using in the color filter of the present invention is used describes.

The example that can be used as the composition of coloring composite for color filter of the present invention comprises that the spy opens the composition of putting down in writing in paragraph numbering [0046]～[0056] of 2004-347831 communique.

In above-mentioned pigment, from obtaining the viewpoint of high color purity and flatness, the R of liquid crystal display device color filter of the present invention (redness) pixel preferably contains C.I. paratonere 254 (C.I.PR-254) at least as pigment.

In addition, from obtaining the viewpoint of high color purity and flatness, the G of above-mentioned color filter of the present invention (green) pixel preferably contain C.I. pigment green 36 (C.I.PG-36) and C.I. pigment yellow 13 8 (C.I.PY-138), C.I. pigment yellow 13 9 (C.I.PY-139), C.I. pigment yellow 150 (C.I.PY-150) at least any one as pigment.

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

The zone that sees through that above-mentioned pigment is is positioned at the long wave side, can realize high color purity.In addition, dispersing of pigments and having good stability has the physical property that is suitable for liquid crystal display device color filter purposes of the present invention.

In color compositions of the present invention, all solids composition quality of the relative composition of content of above-mentioned colorant (pigment) is preferably in the scope of 0.1～70 quality %, more preferably in the scope of 0.5～60 quality, particularly preferably in the scope of 1.0～50 quality %.

Selected as described above pigment is, can be met the preferred G of chroma point (x≤0.32 on the XYZ chromaticity diagram of the illuminant-C that utilizes 3 primary colors of R (redness), G (green), B (blueness), y 〉=0.56), more preferably R (x 〉=0.62, y≤0.35), G (x≤0.32, y 〉=0.56) and the preferred liquid crystal display device color filter of B (x≤0.17, y≤0.14).Like this, the utilization ratio of light backlight is reduced, can realize further improving HDTV specification as the main colourity specification of TV purposes and be R (x=0.64, y=0.33), G (x=0.3, y=0.6), B (x=0.15, y=0.06) and so on high color purity.

The example of the assay method of the chroma point on the XYZ chromaticity diagram of utilizing illuminant-C of color filter comprises the method for using microspectrophotometer to be determined at each pixel that forms on the transparency carrier, perhaps make the pixel of the square size in the 3cm left and right sides, and then with common ultraviolet-visible pectrophotometer method for measuring etc.

In the present invention, preferred pigment optimization uses with the state of dispersion liquid.The example of such dispersion liquid comprises that the spy opens the dispersion liquid of putting down in writing in paragraph numbering [0058]～[0059] of 2004-347831 communique.

The making of color filter

In color filter of the present invention, each the colored pixels group that on the photopermeability substrate, has R (redness), G (green), B (blueness) at least, each pixel that constitutes this pixel groups is the structure of utilizing black matrix to separate each other, and this black matrix uses described black matrix of the present invention to make with coloured composition or photosensitive transfer printing material and makes.It is preferred that wherein redness, green, 3 kinds of blue pixel groups are configured to inlay type, stripe or triangular form etc. at least.

The example of the substrate of described photopermeability is included in the surface and has the known glass plate such as soda-lime glass plate, low-expansion glass plate, alkali-free glass plate, quartz glass plate of monox tunicle or plastic sheeting etc.

The method of making color filter also can be included in utilizes conventional method to form pixel groups more than 2 on the substrate of photopermeability, carry out as described above then, forms the operation of black matrix.Perhaps, also can be included in the black matrix of initial formation, form the operation of the pixel groups more than 2 then.Color filter of the present invention is owing to possessing aforesaid black matrix, so have high demonstration contrast and outstanding flatness.

Below the manufacture method of color filter of the present invention is elaborated.Can make color filter of the present invention with each pixel of R, G, B.The example of this manufacture method can comprise implements following each operation successively.

(1) on substrate, engage contain optical polymerism compound, Photoepolymerizationinitiater initiater, bonding agent, coloring components (pigment) thus the color filter that waits makes the operation that the photosensitive color resin bed is set with the photonasty sheet material of coloured composition formation;

(2) above-mentioned photosensitive color resin bed is exposed into the operation of pattern-like;

(3) the photosensitive color resin bed that develops and to have exposed obtains the operation of the pattern-like color solidification rete that the exposed portion by the photosensitive color resin bed constitutes; And

(4) by heating above-mentioned pattern-like color solidification rete etc., burn till and then make the operation of its curing.

Above-mentioned (1)～(4) operation can be opened the method for putting down in writing in paragraph numbering [0062]～[0065] of 2004-347831 communique with the spy and similarly carry out.

Liquid crystal indicator

A mode of liquid crystal indicator of the present invention is to possess color filter, liquid crystal layer and the liquid crystal drive mechanism element of (comprising simple matrix type of drive or driven with active matrix mode etc.) at least between at least one side is 1 pair of substrate of photopermeability.This color filter has the pixel groups of 3 looks at least.Each pixel that constitutes this pixel groups is separated by black matrix of the present invention each other.So the flatness height of color filter of the present invention is the liquid crystal indicator that possesses this color filter generation unit spacing inequality not between color filter and substrate.So it is bad that look unequal demonstration can not take place.

In addition, another mode of liquid crystal indicator of the present invention is to possess color filter, liquid crystal layer and liquid crystal drive mechanism at least between at least one side is a pair of supporter of photopermeability.This liquid crystal drive mechanism has active component (for example TFT), and possesses the color filter that is formed with 3 color pixel groups and black matrix of the present invention between each active component.

In addition, use the preference of the liquid crystal indicator of the present invention of color filter of the present invention to have 3 wavelength light sources, combination has the pixel of backlight and described R (redness), G (green), B (blueness) 3 primary colors.At this, in liquid crystal indicator of the present invention, 3 primary colors that utilize of preferred R (redness), G (green), B (blueness) utilize chroma point on the XYZ chromaticity diagram of illuminant-C in R (x 〉=0.62, y≤0.35), G (x≤0.32, y 〉=0.56) and the chromaticity range of B (x≤0.17, y≤0.14).

Embodiment

Below based on embodiment to the detailed description of the invention, but the present invention is not limited by these examples.In addition, " part " in the present embodiment, " % " and " molecular weight " short ofly conclude especially, expression " mass parts ", " quality % " and " matter average molecular weight ".

Embodiment 1

The preparation of carbon black dispersion liquid

With electronic grinding machine (trade name: M50 likes lattice (ア イ ガ one) (strain) system), use the zirconium oxide bead of diameter 0.65mm, prepare the carbon black dispersion liquid of following prescription.

69 parts of n-propanols

(copolymerization is than=20: 80) 10 parts for methacrylic acid/ALMA multipolymer

1 part of spreading agent (trade name: ソ Le ス パ one ス 20000, ア PVC シ ア (strain) system)

20 parts of carbon blacks (trade name carbon black MA100, Mitsubishi Chemical's (strain) system)

The making of silver particles

In gelatin 112g, add distilled water 3488g, with the mixture heated that obtains to about 47 ℃, the dissolving gelatin.To wherein adding calcium acetate 4.0g and borane potassium 2.0g.Add the silver nitrate 6.0g that is dissolved among the distilled water 1.0L then immediately apace while stirring.And then, product is cooled near gelling temperature, make it pass through aperture, in chilled water, push, make very fine bar (noodle) thus.Then and there with these supplies as the amplification catalyzer that is used to produce blue silver.For convenience and to prevent that bar from forming fusion fast, dilute with water bar, water and bar are 1: 3.

In borane reduction galactic nucleus 650g, add monosulfonic acid quinhydrones potassium 6.5g and the KCl0.29g that is dissolved among the distilled water 81g.Above-mentioned bar slurry (slurry) is cooled to about 6 ℃.In addition, preparing the 2 kinds of solution (A) with following composition in each container reaches (B).

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

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

Mix above-mentioned solution (A) and reach (B), continue to stir, make it form white precipitate.(in 5 minutes) are stirred this potpourri apace and are added in above-mentioned slurry simultaneously then, immediately at short notice.At 10 ℃, then, amplification was carried out about 80 minutes temperature maintenance, be reduced on the nuclear until all soluble silver salts.Make the blueness slurry particle that obtains via slurry, in the nylon mesh back of the body (nylonmesh back),, then, make rinse water pass through the back of the body (back) and clean about 30 minutes, so whole salt is washed away by tap water.For the blue silver dispersions of the silver that under the situation of fusion, has 1.5 quality % concentration, get rid of the water of the blue silver that is scattered in gel slurry and has cleaned, make the quality of product become 412g.The transmission electron microscope photo shows that this silver is made of the particle of the particle diameter of record in the table.

The preparation of silver particles dispersion liquid

Disperse to add among the slurry 4000g spreading agent (trade name: ラ ピ ゾ one Le B-90, Japanese grease (strain) system) 6g and papain 5% aqueous solution 2000g at the silver that obtains as mentioned above, preserved 24 hours down for 37 ℃ in temperature.With 5 fens clock times,, make the silver particles precipitation with this liquid of 2000rpm centrifuging.After the abandoning supernatant, clean, remove by enzyme and decompose the keratin analyte that obtains with distilled water.Then, with this silver particles sediment of washed with methanol, make its drying then.Can obtain the condensation product of the silver-colored particulate of about 60g.Mix this condensation product 53g and spreading agent (trade name: ソ Le ス パ 1, ア PVC シ ア (strain) system) 5g, methyl ethyl ketone 22g.To wherein mixing 2mm Φ beaded glass 100g, disperseed 3 hours with coating wobbler (paint shaker), obtain the silver particles dispersion liquid (A1) that needs.

To in the above-mentioned silver particles dispersion liquid (A1) that obtains, adding, mixing following additives, obtain silver particles and contain coating liquid.

Above-mentioned silver particles dispersion liquid (A1) 40.0g

Propylene glycol monomethyl ether acetic acid esters 40.0g

Methyl ethyl ketone 37.6g

Fluorine is surfactant 1 (trade name: F-780-F, big Japanese ink (イ Application キ) chemical industry (strain) system, 30% methyl ethyl ketone solution) 0.1g

Quinhydrones monomethyl ether 0.001g

Dipentaerythritol acrylate 2.1g

Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] carbamyl] phenyl] sebacate 0.1g

The light shield layer preparation of coating liquid

Add, be blended in the above-mentioned carbon black dispersion liquid that obtains and contain coating liquid in the above-mentioned silver particles that obtains, the preparation light shield layer is with applying liquid.This light shield layer is formulated into coating liquid and is the mixing (blend) of the carbon black shown in the table 2 (C.B.)/silver particles ratio.

The method for making of photosensitive transfer printing material

On the interim supporter of the pet film of thick 75 μ m, use slot-shaped nozzle, the thermoplastic resin coating liquid that coating, dry following prescription H1 constitute.Then, the middle layer coating liquid that coating, dry following prescription P1 constitute.And then coating, dry above-mentioned light shield layer are with applying liquid.Like this, on interim supporter, the thermoplastic resin of dry film thickness 14.6 μ m, middle layer and the light shield layer of dry film thickness 1.6 μ m are set, press sticking protective film (thick 12 μ m polypropylene films) at last.

Make the dark photosensitive transfer printing material that interim supporter, thermoplastic resin, middle layer (oxygen-proof membrane) and light shield layer become one like this, sample is called photosensitive transfer printing material K1.

Thermoplastic resin is with applying liquid: prescription H1

11.1 parts of methyl alcohol

6.36 parts of propylene glycol monomethyl ether acetic acid esters

52.4 parts of methyl ethyl ketones

Methyl methacrylate/2-ethylhexyl acrylate/methacrylic acid benzyl ester/methacrylic acid copolymer (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=100,000,

) 5.83 parts

Styrene/acrylic acid co-polymer (copolymerization ratio of components (mol ratio)=63/37, molecular weight=10,000,

) 13.6 parts

The compound (2 that obtains to bisphenol-A dehydrating condensation 2 equivalent five ethylene glycol monomethyl acrylate, two [4-(methacryloxy polyethoxy) phenyl] propane of 2-, Xin Zhong village chemical industry (strain) system) 9.1 part

Fluorine is 10.54 parts in a surfactant

The middle layer is with applying liquid: prescription P1

Polyvinyl alcohol (PVA) (trade name: PVA205, (strain) storehouse lira (Network ラ レ) system, saponification degree=88%, the degree of polymerization 550)

32.2 part

14.9 parts of polyvinylpyrrolidones (trade name: K-30, ア イ エ ス ピ one ジ ヤ パ Application (liking lattice Japan) corporate system)

524 parts of distilled water

429 parts of methyl alcohol

Use organosilane coupling agent solution (trade name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) system, 1% dilution) that glass substrate is handled, obtain the organosilane coupling agent and handle glass substrate.

Handle on the glass substrate at the organosilane coupling agent that obtains; remove protective film from the photosensitive transfer printing material that utilizes above-mentioned manufacture method to make; the surface that makes its surface that is overlapped into the light shield layer that exposes after removing and above-mentioned organosilane coupling agent handle glass substrate contacts; use laminator (trade name: LamicII type; (strain) Hitachi industry (イ Application ダ ス ト リ イ ズ) corporate system); to substrate, with 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transporting velocity 2.2m/ minute lamination.Then, with the interim supporter of the interface peel polyethylene terephthalate of thermoplastic resin, remove interim supporter.With the close induction type exposure machine with ultrahigh pressure mercury lamp (Hitachi's high-tech electronic engineering (strain) system), with substrate and the vertical state that erects of mask (quartzy exposed mask) with picture pattern, the distance of setting between exposed mask face and the middle layer is 200 μ m, with exposure 200mJ/cm ²Carry out pattern exposure.

Then, use is that developer solution (contains triethanolamine 30 quality % with pure water dilution triethanolamine, trade name: T-PD2, Fujiphoto (strain) system) to the liquid (30 ℃) of 12 times (mixing with the ratio of 11 mass parts pure water) with 1 mass parts T-PD2, with 50 seconds, flat nozzle pressure 0.04MPa, spray development, remove thermoplastic resin and middle layer.Then, blow above the substrate to this, get rid of after the liquid, utilize spray to blow pure water 10 seconds, carry out the pure water spray Cleaning for High Capacity, blow, the liquid that reduces on the substrate accumulates.

Then, using with 5 times of dilutions of pure water carbonic acid Na is developer solution (sodium bicarbonate, the sodium carbonate of 0.47 mol, the nekal of 5 quality %, anionic surfactant, defoamer, the stabilizing agent that contain 0.38 mol, trade name: T-CD1, Fujiphoto (strain) system) liquid (29 ℃), with 30 seconds, pyramid type nozzle pressure 0.15MPa, spray development, develop and remove photo-sensitive resin, obtain pattern image.

Then, use (contains phosphate silicate non-ionic surfactant defomaing agent stabilizing agent with pure water with clean-out system, trade name: T-SD1 Fujiphoto (strain) system) be diluted to 10 times liquid (33 ℃), with 20 seconds, pyramid type nozzle pressure 0.02MPa, blow with spray, and then utilize rotating brush, the image that wiping forms with nylon hair, remove residue, obtain black matrix.

Then, under atmosphere, utilize aligner alinear (aligner), with 2000mJ/cm ², from the surface of substrate, to substrate carry out post-exposure comprehensively, 220 ℃ of thermal treatments of implementing 30 minutes down, obtain the black matrix of embodiment 1.

In addition, each light shield layer is mixed with mixing ratio and then the use with the carbon black/silver particles shown in the table 2 with coating liquid, in addition, carries out similarly to Example 1, obtain the black matrix of embodiment 2～4 and embodiment 7,8 and 12.

The making of color filter

The making of photosensitive resin transfer material

With making identical method with above-mentioned photosensitive transfer printing material K1, use the described photosensitive composition of following table 1, make photosensitive transfer printing material R, photosensitive transfer printing material G, photosensitive transfer printing material B.

The formation of red (R) pixel

Exposure in exposure process is altered to 40mJ/cm ²With carbonic acid Na be the spray of developer solution develop be altered to 35 ℃ following 35 seconds, and with thermal treatment be altered to 220 ℃ following 15 minutes, in addition, carry out the operation identical with the formation of described black matrix, use described photosensitive resin transfer material R, hide a side of deceiving matrix being formed with of glass substrate and form red (R) pixel.

The thickness of R pixel is 2.0 μ m, and the coating amount of C.I. paratonere (C.I.P.R.) 254, C.I.P.R.177 is respectively 0.88g/m ², 0.22g/m ²

Then, use clean-out system more as described above, scrub the glass substrate that is formed with the R pixel, after cleaning with pure water, do not use organosilane couplant liquid, utilize the basal plate preheating device, under 100 ℃, heated 2 minutes.

The formation of green (G) pixel

Exposure in exposure process is altered to 40mJ/cm ²With carbonic acid Na be the spray of developer solution develop be altered to 34 ℃ following 45 seconds, and with thermal treatment be altered to 220 ℃ following 15 minutes, in addition, carry out the operation identical with the formation of described R pixel, use the above-mentioned photosensitive resin transfer material grain G that obtains, a side that hides black matrix and R pixel being formed with of glass substrate forms green pixel (G pixel).

The thickness of G pixel is 2.0 μ m, and the coating amount of C.I. naphthol green (C.I.P.G.) 36, C.I. pigment yellow (C.I.P.Y.) 150 is respectively 1.12g/m ², 0.48g/m ²

Then, use clean-out system more as described above, scrub the glass substrate that is formed with black matrix, R pixel and G pixel, after the pure water spray Cleaning for High Capacity, do not use organosilane couplant liquid, utilize the basal plate preheating device, under 100 ℃, heated 2 minutes.

The formation of blue (B) pixel

Exposure in exposure process is altered to 30mJ/cm ²With carbonic acid Na be the spray of developer solution develop be altered to 36 ℃ following 40 seconds, in addition, carry out the operation identical with the formation of described R pixel, use the above-mentioned photosensitive resin transfer material B that obtains, form blue pixel (B pixel) in a side of the black matrix of being formed with of glass substrate and R pixel and G pixel.

The thickness of B pixel is 2.0 μ m, and the coating amount of C.I. alizarol saphirol (C.I.P.B.) 15:6, C.I. pigment violet (C.I.P.V.) 23 is respectively 0.63g/m ², 0.07g/m ²

Then, under 240 degree, cure the glass substrate 50 minutes of each pixel that is formed with R, G, B, obtain color filter.

[table 1]

Photosensitive composition	R	G	B
				R pigment dispersing thing 1 (C.I.P.R.254)	44	-	-
R pigment dispersing thing 2 (C.I.P.R.177)	5.0	-	-
				G pigment dispersing thing 1 (C.I.P.G.36)	-	24	-
Y pigment dispersing thing 1 (C.I.P.Y.150)	-	13	-
				B pigment dispersing thing 1 (C.I.P.B.15:6)	-	-	7.2
B pigment dispersing thing 2 (C.I.P.B.15:6+C.I.P.V.23)	-	-	13
				Propylene glycol monomethyl ether acetic acid esters	7.6	29	23
Methyl ethyl ketone	37	26	35
				Cyclohexanone	-	1.3	-
Bonding agent-1	-	3	-
				Bonding agent-2	0.8	-	-
Bonding agent-3	-	-	17
				DPHA liquid	4.4	4.3	3.8
2-trichloromethyl-5-(to the styryl styryl) 1,3, the 4-oxadiazole	0.14	0.15	0.15
				2, two (the trichloromethyl)-6-[4 ' of 4--(N, the two ethoxy carbonyl methylaminos of N-)-3 '-bromophenyl]-the s-triazine	0.058	0.060	-
Phenothiazine	0.010	0.005	0.020
				Adjuvant 1	0.52	-	-
Above-mentioned fluorine is a surfactant 1	0.060	0.070	0.050

Unit: mass parts

In the table 1, bonding agent 2 composed as follows described.

Polymkeric substance (methacrylic acid benzyl ester/methacrylic acid=78/22[mol ratio] random copolymers, molecular weight: 3.8 ten thousand) 27 parts

73 parts of propylene glycol monomethyl ether acetic acid esters

DPHA liquid composed as follows described.

Dipentaerythritol six acrylic acid

(contain anti-polymerizer MEHQ 500ppm, Japanese chemical drug (strain) system, trade name: KAYARAD DPHA) 76 parts

24 parts of propylene glycol monomethyl ether acetic acid esters

R pigment dispersing thing 1 composed as follows described.

8 parts of C.I.P.R.254 (the red B-CF of trade name: Irgaphor, the special chemicals of Chiba (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ) (strain) system)

1 0.8 parts of following compounds

8 parts in polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=73/27 mol ratio)

83 parts of propylene glycol monomethyl ether acetic acid esters

Compound 1

[changing 1]

R pigment dispersing thing 2 composed as follows described.

C.I.P.R.177 (the red A2B of trade name: Cromophtal, the special chemicals of Chiba (strain) system)

12 parts in polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=73/27 mol ratio)

70 parts of propylene glycol monomethyl ether acetic acid esters

Bonding agent 1 composed as follows described.

27 parts in polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid/methyl methacrylate=38/25/37 mol ratio, molecular weight 40,000)

73 parts of propylene glycol monomethyl ether acetic acid esters

Adjuvant 1 for phosphate be special activators (trade name: HIPLAAD ED152, nanmu originally change into (strain) system).

As G pigment dispersing thing 1, use GT-2 (trade name, Fujiphoto electronics synthesis material (Off イ Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ) (strain) system).

As Y pigment dispersing thing 1, use the yellow EX3393 of CF (trade name is driven state's pigment (strain) corporate system).

As B pigment dispersing thing 1, use the blue EX3357 of CF (trade name is driven state's pigment (strain) corporate system).

As B pigment dispersing thing 2, use the blue EX3383 of CF (trade name is driven state's pigment (strain) corporate system).

In addition, bonding agent 3 is composed as follows described.

Polymkeric substance (methacrylic acid benzyl ester/methacrylic acid/methyl methacrylate

The random copolymers of=36/22/42 mol ratio, molecular weight 3,8 ten thousand) 27 part

73 parts of propylene glycol monomethyl ether acetic acid esters

Embodiment 5 and 6

The formation of black matrix

Each light shield layer is mixed with mixing ratio and then the use with the carbon black/silver particles shown in the table 2 with coating liquid, in addition, utilize operation similarly to Example 1, coating on glass substrate, dry light shield layer are formed on the photonasty light shield layer that uses in embodiment 5 and 6 with coating liquid.

Then, use ultrahigh pressure mercury lamp, above-mentioned photonasty light shield layer is carried out 500mJ/cm ²Pattern exposure.Then, as developer solution, use with 5 times of dilutions of pure water contain nekal, anionic surfactant, the defoamer of sodium carbonate, the 5 quality % of sodium bicarbonate, 0.47 mol of 0.38 mol, the sodium carbonate of stabilizing agent is developer solution (trade name: T-CD1, Fujiphoto (strain) system) liquid (29 ℃), the light sensitive black resin bed of development light shield layer, remove unexposed portion, embodiment 5 that formation needs and 6 black matrix.Then, carry out similarly to Example 1, make the color filter of embodiment 5 and 6.

Embodiment 9

" light shield layer is with applying liquid " that to use in embodiment 1 is altered to " silver/silver sulfide contains light shield layer with applying liquid ", in addition, carries out similarly to Example 1, makes the color filter shown in the table 3.

The making of silver/silver sulfide core-shell particles

Disperse to add among thing (mean grain size 30nm, the concentration 2.5 quality %) 200g vinyl pyrrolidone/vinyl acetate co-polymer (=60/40[mass ratio], molecular weight 5000) 0.95g to the acetone of silver particles, stirred 30 minutes.Then, to wherein adding the sodium sulfide solution that concentration is 7.2 quality % (23 ℃), make the sulfuration rate of metal become 30% while stirring, after add finishing, directly carry out stirring in 30 minutes, obtain having the silver/silver sulfide core-shell particles of the shell of silver sulfide.

At this, the sulfuration rate is meant the sulfureted ratio of metallics.The sulfuration rate is that 0% expression does not have sulfureted state fully, and the whole particle of sulfuration rate 100% expression fully becomes the state of sulfide.

Embodiment 10

Replace silver particles to use the tin particle, in addition, use the method identical, make the tin particle, carry out similarly to Example 1, make the color filter shown in the table 3 with embodiment 1.

Embodiment 11

Light shield layer is altered to following silver-colored ashbury metal with coating liquid contains light shield layer, in addition, carry out similarly to Example 1, make the color filter shown in the table 3 with coating liquid.

The preparation of AgSn alloy particle dispersion liquid (dispersion liquid A1)

In pure water 1000ml, dissolve silver acetate (I) 23.1g, tin acetate (II) 65.1g, gluconic acid 54g, sodium pyrophosphate 45g, polyglycol (molecular weight 3,000) 2g and E735 (ISP corporate system; Vinyl pyrrolidone/vinyl acetate co-polymer) 5g obtains solution 1.

In addition, dissolving hydroxypropanone-36.1g obtains solution 2 in pure water 500ml.

The above-mentioned solution that obtains 1 is remained on 25 ℃ and stir tempestuously, use 25 minutes simultaneously,, continue to stir lentamente the potpourri 6 hours that this interpolation obtains to wherein adding above-mentioned solution 2.Like this, this mixed liquor becomes black, obtains Yin Xi (AgSn) alloy particle.Then, this mixed liquor of centrifuging makes this AgSn alloy particle precipitation.This centrifugal separation process is the aliquot that this potpourri is divided into liquid measure 150ml, utilizes desk-top centrifugal separator (trade name: H-103n, (strain) コ Network サ Application system), and with rotating speed 2,000r.p.m. carried out 30 minutes.After this centrifuging, discard the supernatant in the sample, make whole liquid measures become 150ml.In this sample, add pure water 1350ml, stirred 15 minutes, described AgSn alloy particle is disperseed once more.Repeat this precipitation and scatter operation 2 times, go out the solable matter of water.

Then, further carry out centrifuging, described AgSn alloy particle is precipitated once more.Under above-mentioned identical condition, carry out centrifuging.After this centrifuging,, make whole liquid measures become 150ml, to wherein adding pure water 850ml and acetone 500ml, and then stirred 15 minutes, described AgSn alloy particle is disperseed once more with above-mentioned supernatant discarded similarly.

Similarly carry out centrifuging with above-mentioned once more, make AgSn alloy particle precipitation, then with above-mentioned supernatant discarded similarly, make liquid measure become 150ml, to wherein adding pure water 150ml and acetone 1200ml, and then stirred 15 minutes, described AgSn alloy particle is disperseed once more.Then, separation once more.The condition of centrifuging of this moment is with time lengthening to 90 minute, and is in addition, same as described above.Then, supernatant discarded makes whole liquid measures become 70ml, to wherein adding acetone 30ml.(trade name: M-50 type (medium: diameter 0.65mm zirconium oxide bead 130g), ア イ ガ one ジ ヤ パ Application (strain) is made) with its dispersion 6 hours, obtains Yin Xi (AgSn) alloy particle dispersion liquid to use ア イ ガ one ミ Le.Observe the result of this particle dispersion liquid with transmission electron microscope, disperse mean grain size to be about 40nm with the number average particle size.

The silver ashbury metal contains the preparation of light shield layer with coating liquid

Mix following composition, prepare silver-colored ashbury metal and contain light shield layer with applying liquid.

Above-mentioned AgSn alloy particle dispersion liquid (A1) 50.00g

Propylene glycol monomethyl ether acetic acid esters 28.6g

Methyl ethyl ketone 37.6g

Described fluorine is surfactant 0.2g

Quinhydrones monomethyl ether 0.001g

9.6 parts of styrene/acrylic acid co-polymer (mol ratio=56/44, weight-average molecular weight 30,000)

Dipentaerythritol acrylate (trade name: KAYARAD DPHA, Japanese chemical drug corporate system) 9.6g

Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] carbamyl] phenyl] sebacate 0.5g

Comparative example 1～4

With the method identical with embodiment 1, the addition of modulation carbon black, silver particles etc. are made the color filter shown in the table 3.

In each color filter that obtains, measure TFT lateral reflection rate, see through optical concentration, per unit thickness see through optical concentration, R, G, the thickness of B, Film Thickness Ratio (TR/BM, TG/BM and TB/BM), jut height, colourity, demonstration inequality, the result is shown in table 2 and table 3.

The making of liquid crystal indicator

On the R of each colour filtering chip basic board that utilizes the foregoing description and comparative example to obtain pixel, G pixel and B pixel and black matrix, further utilize sputter to form the transparency electrode of indium tin oxide (ITO:IndiumTin Oxide).Then, the embodiment 1 according to the spy opens the 2006-64921 communique forms distance piece in the part that is equivalent to the top, next door (black matrix) on the ITO film of above-mentioned formation.

In addition, prepare glass substrate again as counter substrate.To implementing the PVA pattern respectively and form on the transparency electrode of colour filtering chip basic board and on the counter substrate, the alignment films that polyimide constitutes is set further thereon with pattern.

Then, be arranged to surround the position of housing of black matrix of the pixel groups of color filter around be equivalent to, utilize decollator (dispenser) mode, the sealant of coating ultraviolet curable resin, the PVA pattern of dripping liquid crystal makes itself and counter substrate applying.Carry out the UV irradiation to the substrate of having fitted, heat-treat then, make sealant cures.On the two sides of the liquid crystal cells that obtains like this, stick polaroid (trade name: HLC2-2518, (strain) three upright magnetic (サ Application リ Star Star) systems).Then, use red (R) LED of FR1112H (sheet (chip) the type LED that Stanley's (ス タ Application レ one) electric (strain) makes) conduct, use DG1112H (sheet (chip) the type LED of ス タ Application レ one electric (strain) system) conduct green (G) LED, use DB1112H (sheet (chip) the type LED of Stanley's electric (strain) system), the backlight of formation side lamp mode as blueness (B) LED.This backlight is configured in a side at the back side that becomes the liquid crystal cells that is provided with described polaroid, makes liquid crystal indicator.

Evaluation method

Determining film thickness

Use contact surfagauge (trade name: P-1, TENCOR company (strain) system), measure each the black matrix of formation after curing or the thickness of colored pixels.

Measure the optical concentration that sees through of black matrix with following method.

At first, use the material that in embodiment and comparative example, forms black matrix, use described ultrahigh pressure mercury lamp, from the applicator surface side, to be set as OD be that the light shield layer of the film below 3.0 carries out 500mJ/cm being coated with on the glass substrate ²Exposure.Then, use Macbeth densimeter (trade name: TD-904, Macbeth corporate system), measure this optical concentration (O.D.).In addition, see through optical concentration (OD with what identical method was measured glass substrate ₀).Use contact surfagauge (trade name: P-1, KLI TENCOR (ケ one エ Le エ one テ Application コ one Le) company's (strain) system), measure thickness, will deduct OD from above-mentioned OD with sample ₀The value of gained from the relation that sees through optical concentration and thickness of this measurement result, is calculated the optical concentration of the black matrix of the thickness of making in an embodiment as the optical concentration that sees through of light shield layer.

TFT lateral reflection rate is measured

With spectrophotometer (spectrphotometer) (trade name: V-560, Japan's beam split (strain) system) the absolute reflectance determinator (trade name: ARV-474 of combination, Japan's beam split (strain) system), measure the absolute reflectance of (being formed with the face of coated film) of TFT lateral reflection rate.

Measuring angle is 5 degree from vertical direction, and wavelength is 555nm.

Particle diameter (nm) is measured

Utilize transmission electron microscope (trade name: JEM-2010,200000 times of multiplying powers, NEC (strain) system), measure 100 particles, be converted into projected area circle of the same area, its diameter as particle diameter, is worth mean value as this.

The mensuration of colourity

Use microspectrophotometer (trade name: OSP100, Olympus Optical Co., Ltd system), be determined at the colourity of the above-mentioned color filter that obtains with hole diameter 5 μ m, the result who spends as the illuminant-C visual field 2 calculates.

Show colour mixture

In embodiment and comparative example, redness (R), green (G), blue (B) develop the colors simultaneously, with the naked eye measure certain area (interior density unevenness of scope of 10cm * 10cm).This judges by 10 people and implements, and the number that is judged as density unevenness is under 0 the situation, to be evaluated as A, and this number is under 1～2 people's the situation, is evaluated as B, and this number is under the above situation of 3 people, be evaluated as *.

The misoperation of TFT

The part of the backlight of LCD becomes the incident light to TFT, the leak light when becoming black display in black matrix layer surface reflection.To there be this leak light to be evaluated as misoperation.Represent that in table 2 and table 3 it has or not.In the dark confirm to estimate leak light.

Show uneven

When in liquid crystal indicator, importing the test signal of ash (gray), observe, judge uneven having or not with visual and amplifying lens (Lupe).

[table 2]

Sample No.	Comparative example 1	Comparative example 2	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
									Black matrix formation method	Transfer printing	Transfer printing	Transfer printing	Transfer printing	Transfer printing	Transfer printing	LR ※	LR ※
Carbon black	Contain	Contain	Contain	Contain	Contain	Contain	Contain	Contain
									Metallics	Do not have and add	Silver particles	Silver particles	Silver particles	Silver particles	Silver particles	Silver particles	Silver particles
C.B/ metallics mixing ratio	-	5.50	2.64	1.32	1.32	1.32	1.32	1.32
									TFT lateral reflection rate (%)	0.5	0.5	0.5	1.5	1.5	1.5	1.5	1.5
See through optical concentration	4.0	4.0	4.0	4.2	4.2	4.2	4.2	4.2
									Particle diameter (nm)	-	80	80	80	80	80	80	80
Thickness (μ m)	2.00	1.33	1.08	0.76	0.76	0.76	0.76	0.76
									The per unit thickness see through optical concentration [seeing through optical concentration/whole thickness]	2.0	3.0	3.7	5.5	5.5	5.5	5.5	5.5
R.G.B. thickness (μ m)	1.5	1.5	1.5	1.5	2.0	2.5	1.5	1.5
									Film Thickness Ratio (R.G.B./BK)	0.8	1.1	1.4	2.0	2.6	3.3	2.0	2.0
Difference of height on the BK (μ m)	0.7	0.5	0.3	0.1	0.1	0.0	0.1	0.1
									The TFT misoperation	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have
Tone: B (scope: x＜0.17, y＜0.14)	Outside the scope	Outside the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope
									Show colour mixture	x	x	B	A	A	A	A	A
B colourity (x)	0.20	0.19	0.17	0.16	0.15	0.15	0.16	0.16
									B colourity (y)	0.17	0.14	0.08	0.06	0.06	0.06	0.07	0.07
Tone: G (scope: x＜0.32, y＞56)	Outside the scope	Outside the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope
									G colourity (x)	0.35	0.33	0.30	0.30	0.30	0.30	0.30	0.30
G colourity (y)	0.51	0.54	0.58	0.58	0.58	0.58	0.58	0.58
									Tone: R (scope: x＞0.62, y＜0.35)	Outside the scope	Outside the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope
R colourity (x)	0.57	0.60	0.63	0.64	0.64	0.64	0.64	0.64
									R colourity (y)	0.37	0.37	0.34	0.34	0.34	0.34	0.34	0.34
Show uneven	Have	Have	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have

LR ※: the development method that uses liquid resist

[table 3]

Sample No.	Embodiment 7	Embodiment 8	Comparative example 3	Comparative example 4	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12
									Black matrix formation method	Transfer printing	Transfer printing	Transfer printing	Transfer printing	Transfer printing	Transfer printing	Transfer printing	Transfer printing
Carbon black	Contain	Contain	Contain	Do not have and add	Contain	Contain	Contain	Contain
									Metallics	Silver particles	Silver particles	Silver particles	Silver particles	Silver silver sulfide nucleocapsid	Sn	Silver ashbury metal particle	Silver particles
C.B/ metallics mixing ratio	0.88	0.33	0.10	0.00	1.32	1.32	1.32	1.32
									TFT lateral reflection rate (%)	2.6	4.0	15	20	0.5	0.5	0.5	1.5
See through optical concentration	4.5	5.0	4.0	4.0	3.9	4.0	3.8	4.0
									Particle diameter (nm)	80	80	80		90	36	40	117
Thickness (μ m)	0.78	0.60	0.60	0.50	0.80	0.90	0.70	0.60
									The per unit thickness see through optical concentration [seeing through optical concentration/whole thickness]	5.8	8.3	6.7	8.0	4.9	4.4	5.4	6.7
R.G.B. thickness (μ m)	1.5	2.5	1.5	1.5	1.5	1.5	1.5	1.5
									Film Thickness Ratio (R.G.B./BK)	1.9	4.2	2.5	3.0	1.9	1.7	2.1	2.5
Difference of height on the BK (μ m)	0.1	0.0	0.0	0.0	0.1	0.1	0.1	0.0
									The TFT misoperation	Do not have	Do not have	Have	Have	Do not have	Do not have	Do not have	Do not have
Tone: B (scope: x＜0.17, y＜0.14)	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope
									Show colour mixture	A	A	A	A	A	A	A	A
B colourity (x)	0.16	0.15	0.15	0.15	0.16	0.16	0.16	0.16
									B colourity (y)	0.07	0.06	0.06	0.06	0.07	0.07	0.07	0.07
Tone: G (scope: x＜0.32, y＞56)	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope
									G colourity (x)	0.30	0.29	0.29	0.29	0.30	0.30	0.30	0.30
G colourity (y)	0.60	0.60	0.60	0.60	0.58	0.58	0.58	0.58
									Tone: R (scope: x＞062, y＜0.35)	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope	In the scope
R colourity (x)	0.65	0.65	0.65	0.65	0.64	0.64	0.64	0.64
									R colourity (y)	0.34	0.34	0.34	0.34	0.34	0.34	0.34	0.34
Show uneven	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have	Do not have

From the following as can be known situation of the result of table 2, table 3.

Even make the thickness attenuation of black matrix, the color filter of embodiment see through the also high and per unit thickness of optical concentration to see through optical concentration also high, and colourity is good, shows unevenly, TFT lateral reflection rate is low, so contrast is outstanding.

Utilizability on the industry

Liquid crystal display device color filter of the present invention and the liquid crystal indicator display comparison degree in the room is outstanding, does not have the misoperation of TFT, shows inequality, and can realize simultaneously high color purity and high permeability.

Claims (12)

1. liquid crystal display device color filter, it comprises transparency carrier and is arranged at black matrix on this transparency carrier, it is characterized in that,

Contain the green coloring pixel in the zone that this black matrix is separated,

Part on this black matrix is laminated with the part of the dyed layer of this green coloring pixel,

Should black matrix contain pigment and from metallics and metallic compound particle, select at least a,

The content B of the pigment in this black matrix relatively the ratio of the content A of this metallics and metallic compound particle in 0.2～10 scope,

The Film Thickness Ratio of the thickness TG of this green coloring pixel and the thickness BM of black matrix is in 1.2～10 scope.

2. liquid crystal display device color filter according to claim 1 is characterized in that,

The zone of separating at this black matrix also comprises red colored pixel and blue-colored pixel,

The thickness TR of this red colored pixel and the Film Thickness Ratio of described BM be in 1.2～10 scope,

The thickness TB of this blue-colored pixel and the Film Thickness Ratio of described BM are in 1.2～10 scope.

3. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

The jut that the part of the dyed layer of the stacked colored pixels of a part on described black matrix forms is color pixel and the height of projection is below the 0.4 μ m vis-a-vis.

4. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

The penetrating concentration of described black matrix is more than 3.5 and thickness is below the 1.3 μ m.

5. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

Chroma point on the XYZ chromaticity diagram of utilizing illuminant-C of the green of described record is in the G chromaticity range, and described G chromaticity range is the chromaticity range of x≤0.32, y 〉=0.56.

6. liquid crystal display device color filter according to claim 2 is characterized in that,

Chroma point on the XYZ chromaticity diagram of the illuminant-C that utilizes 3 primary colors of the redness of described record, green, blueness is in the chromaticity range of R, G and B, the chromaticity range of described R is the chromaticity range of x 〉=0.62, y≤0.35, the chromaticity range of described G is the chromaticity range of x≤0.32, y 〉=0.56, and the chromaticity range of described B is the chromaticity range of x≤0.17, y≤0.14.

7. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

Described pigment contains select at least a from carbon black and graphite.

8. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

Metallics that contains in the described black matrix or metallic compound particle are metallics.

9. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

Metallics that contains in the described black matrix or metallic compound particle contain select at least a from Ag particulate and AgSn alloy particle.

10. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

Described black matrix comprises: at least a photosensitive polymer combination that contains described pigment and select from described metallics and metallic compound particle.

11. liquid crystal display device color filter according to claim 1 and 2 is characterized in that,

Described black matrix comprises: at least a photosensitive transfer printing material that contains described pigment and select from described metallics and metallic compound particle.

12. a liquid crystal indicator is characterized in that,

Comprise: any described liquid crystal display device color filter in the claim 1～11.

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