CN101178453A

CN101178453A - Color filter as well as liquid crystal display device and CCD device

Info

Publication number: CN101178453A
Application number: CNA2007101637943A
Authority: CN
Inventors: 松本圭右; 横山裕
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2006-11-08
Filing date: 2007-11-08
Publication date: 2008-05-14
Also published as: TW200829965A; KR20080042001A; JP2008139858A

Abstract

The invention provides a color filter which has high light resistance and high contrast(ratio) at the same time, can improve the pixel display performance of the display device, and can restrain the deterioration of the high display performance. Furthermore, the invention provides a liquid crystal display device which uses the color filter with high quality and can exert the excellent pixel display performance and a CCD apparatus. The color filter is formed by the dispersed matters of organic pigment mote; after being irradiated by 0.1 million lux of xenon light for 150 hours, the survival rate of the pigment is 60 to 95 percent; furthermore, the color filter has a pixel whose contrast is bigger than or equal to 5000 before being irradiated by the xenon light.

Description

Color filter, liquid crystal indicator and CCD device

Technical field

The present invention relates to a kind of color filter and use its liquid crystal indicator and CCD device.The present invention relates to a kind ofly have high-contrast and can suppress image when showing owing to burn liquid crystal indicator and the CCD device that shields the high color filter of the bad display quality of the demonstration that causes and use it.

Background technology

In recent years, the image quality of liquid crystal indicator (LCD) etc. is improved, and develops towards the direction with the extensive use that replaces common display CRT (cathode-ray tube (CRT)), and the requirement of improved properties such as color reproduction scope or brightness is further improved.In order to adapt to such requirement, color filter is crucial component materials.This is because color filter is being brought into play painted function on the display image of LCD flat panel or CCD device etc., about the color and luster characteristic of LCD flat panel or CCD device, their basic display performance is produced very big influence.

As the desired characteristic of color filter, for example have: permeability, colour purity, contrast, low reflectivity etc.Particularly, if the permeability of color filter and contrast are low, light will be decayed, thereby display deepening or light and shade are not understood.Therefore the permeability of expecting color filter is high.But also expectation makes the color reproduction scope wideer after making up with RGB, and each colour purity is higher.

For this point, if only want to improve the transmitance of color filter, the particle diameter of pigment is the smaller the better so.If but to do like this, when using it for display panel, demonstration condition of poor such as generation burning screen just become easily and increase.That is,, can make display characteristic produce the tendency that descends on the contrary if merely improve the transparency, contrast.But also to consider that photostability and color and luster are inhomogeneous, existing before this color filter can not satisfy such requirement at all.

In addition, pigment has distinct color, high colouring power, photostability etc., can be used for color filter.In the middle of pigment, most important pigment generally is those pigment with minuteness particle in the practicality.They can prevent the cohesion of pigment and obtain distinct color and high colouring power by miniaturization.But when for example adopting salt mill physical methods such as (salt milling) to make the pigment miniaturization, surface area has increased, but the photostability equistability also worsens easily.

In order to improve these shortcomings, thereby the flowability of obtaining, dispersed good dispersible pigment dispersion or coloring photosensitive combination, known have the surface of pair organic pigment to handle (for example referring to patent documentation 1 and 2) or use the method for various spreading agents (for example referring to patent documentation 3 and 4).In addition, also describe the sample that will be dissolved in good solvent in the patent documentation 5 and 6 and be injected into the reprecipitation method that obtains particle in the poor solvent.

But when the coloring photosensitive combination, its coating and also requires to demonstrate high colour saturation generally as thin as a wafer under the very thin situation of this coating with these pigment.So, for example be necessary to make that the organic pigment of miniaturization disperses with high concentration in organic solvent.The difficulty more because concentration height, aforementioned stableization just become is so real current situation is that pigment that can satisfy these requirements and the color filter that uses it are not provided as yet.

Photostability about organic pigment, though example is arranged the water-base ink that contains yellow uitramarine is being attempted improveing (for example referring to patent documentation 7), but,, do not obtain as yet up to now paying close attention to the photostability that is scattered in the organic pigment in the organic solvent and the relation between the display characteristic.

[patent documentation 1] Japanese kokai publication hei 11-269401 communique

[patent documentation 2] Japanese kokai publication hei 11-302553 communique

[patent documentation 3] Japanese kokai publication hei 8-48890 communique

[patent documentation 4] TOHKEMY 2000-239554 communique

[patent documentation 5] TOHKEMY 2004-123853 communique

[patent documentation 6] TOHKEMY 2003-336001 communique

[patent documentation 7] TOHKEMY 2003-147223 communique

Summary of the invention

Invent problem to be solved

Only from present situation about confirming, be low to moderate 2000～4000 o'clock based on the contrast (ratio) of the color filter of pigment, in practicality, can be described as inadequate.According to the situation that the present inventor confirmed, the method that adopts present widely used microballon dispersion or salt mill is to obtain having the liquid crystal indicator color filter of high-contrast, not only can make the photostability variation, but also can significantly damage display characteristic, the result can not be met the color filter of requirement.

Therefore the object of the present invention is to provide the color filter of the deterioration of a kind of pixel display performance that has high-light-fastness and high-contrast (ratio) simultaneously and can improve display device, the high display performance of inhibition.And, the present invention also aims to provide a kind of liquid crystal indicator and CCD device that uses the good pixel display performance of can bringing into play of high-quality color filter.

The means of dealing with problems

Solve the problems referred to above by following means.

(1) a kind of color filter, it is characterized in that, this color filter is formed by the dispersion thing of organic pigment particulate, in air, be that the survival rate of xenon rayed described pigment after 150 hours of 100,000 luxs is 60～95% with illuminance, and this color filter has contrast for more than or equal to 5000 pixel before the xenon rayed.

(2) color filter described in above-mentioned (1) is characterized in that, described organic pigment particulate is made of red pigment.

(3) color filter described in above-mentioned (1) or (2) is characterized in that, the survival rate of described pigment is 75～90%.

(4) any described color filter in above-mentioned (1)～(3) is characterized in that the contrast before described xenon rayed is more than or equal to 10000.

(5) any described color filter in above-mentioned (1)～(4) is characterized in that the contrast of the red pixel of color filter is more than or equal to 10000 before described xenon rayed.

(6) a kind of liquid crystal indicator is characterized in that, has any described color filter in above-mentioned (1)～(5).

(7) liquid crystal indicator described in above-mentioned (6) is characterized in that, described liquid crystal indicator is the VA mode.

(8) a kind of CCD device is characterized in that, has any described color filter in above-mentioned (1)～(5).

The invention effect

Color filter of the present invention has realized having simultaneously high-contrast and the photostability more than 5000, when being used for display device, can bring into play high display performance, can suppress owing to burn the deterioration that screen waits the display performance that causes.And, possess the liquid crystal indicator of above-mentioned good color filter and CCD device and can realize that bright image shows, and can suppress to show the generation of non-uniform phenomenon.

Embodiment

Below describe the present invention in detail.

Contain the organic pigment particulate in the dyed layer of color filter of the present invention (pixel), this pigment particle in air with illuminance be the survival rate of xenon rayed pigment after 150 hours of 100,000 luxs be 60～95%, be preferably 70～90% survival rate, more preferably 75～90% survival rate, be preferably 80～90% survival rate especially.Herein, " survival rate " is meant that (i) measures the absorption spectrum of color filter or specific pixel before exposure, to point out out by the given peak that pigment produced, calculate its peak area, (ii) follow, exposing (in air, the xenon light that with illuminance is 100,000 luxs shines from glass substrate one side) afterwards, calculate the area at the peak in the absorption spectrum that pigment produced same as described above, (iii) " peak area after the exposure " is divided by " peak area before the exposure " resulting value (ratio).

Described pigment survival rate for example can be tried to achieve by following light fastness test, and what this test was adopted is by the formed color filter of pixel.That is, on glass substrate, form pixel, form color filter after the ITO electrode is set, when this color filter is tested,, remove glass substrate with hydrofluoric acid solution in order can in air, to measure.Can calculate the survival rate of pigment at the ratio before and after the xenon rayed according to the optical concentration of each pixel.

Among the present invention, the thickness of dyed layer (pixel) is preferably 0.5～5 μ m, 1～3 μ m more preferably.In addition, the size of a pixel is preferably 400～90000 μ m ², 1000～15000 μ m more preferably ²

Color filter of the present invention can be used as the color filter of contrast excellence and uses.In the present invention, contrast is meant between two polaroids, the ratio of the light transmission capacity the when light transmission capacity when polarizing axis is parallel is vertical with polarizing axis (referring to " nineteen ninety the 7th the color reversion glory learn コ Application Off アレ Application ス; 512 colour specifications 10.4 " サイズ TFT-LCD is with カラ-Off イ Le , plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).

Use small-sized cold-cathode tube light source, measure the zone that the TFCAM-7000 of system (trade name) measures about 60 μ m at back light unit with the micro-spectral of ラ system ダ PVC ジョ Application Co., Ltd. manufacturing, detect by light only, measure red pixel contrast alone the red pixel that sees through color filter.

The rate of distinguishing of light and shade was big when the contrast height of color filter or described pixel meaned color filter and liquid crystal combination, and this is a very important performance when replacing CRT with LCD.

Color filter of the present invention in above-mentioned light fastness test, the contrast before the xenon rayed for more than or equal to 5000, be preferably more than and equal 10000, be preferably more than especially and equal 15000.In addition, when color filter of the present invention only is red pixel, in above-mentioned light fastness test, the contrast before the xenon rayed for more than or equal to 5000, be preferably more than and equal 10000, be preferably more than especially and equal 15000.

Organic pigment particulate used in the color filter of the present invention preferably uses with the dispersion thing of organic pigment particulate.Manufacture method as the organic pigment particulate, be kind or purpose performance according to pigment, the preferable methods of from methods such as vapor phase method, comminuting method, reprecipitation method, laser ablation method, suitably selecting, consider from accessing the aspect fine and pigment particle that size distribution is even, dispersion stabilization is good, preferably adopt particulate deposition method described later.

In the employed organic pigment of color filter of the present invention, also preferably use Diketopyrrolo-pyrrole compounds pigment.

With the pyrrolopyrrole compound pigment of C.I. paratonere 254,255,264 representatives owing to have for the suitable absorption region of the colour purity that improves the red pixel that forms color filter, and can expand the color reproduction zone, so attempting using it for color filter.But the color and luster purity of existing pigment or contrast etc. can not meet the demands.For example, can not obtain good color filter the ink for inkjet of putting down in writing in the TOHKEMY 2003-336001 communique, employing microballon disperse or the resulting material of method of salt mill etc.

According to the present invention, can obtain size distribution is the nano level pyrrolopyrrole compound pigment particle of pointed distribution.And, when these pigment particles are used for color filter, can take into account desired color and luster purity and high-contrast simultaneously, and photostability is good, can inhibition of sintering screen.And possess the liquid crystal indicator of such color filter, its black density and redness describe power good, and can suppress to show inhomogeneous.

In above-mentioned Diketopyrrolo-pyrrole compounds pigment, preferred C.I. paratonere 254 (compound of following formula (Z) expression), 255 (compounds of following formula (W) expression), 264 (compounds of following formula (V) expression) are from more preferably C.I. paratonere 254 of absorption spectrum.

Also have, as C.I.P.R.254, can use Irgaphor Red B-CF (チバ. スペシヤ Le テイケミカ Le ズ Co., Ltd. makes), Cromophtal DPP RedBO, Irgazin DPP Red BO, Microlen DPP Red BP etc.As C.I.P.R.255, can use Cromophtal Coral Red C, Irgazin DPP Red 5G etc.As C.I.P.R.264, can use (being trade name) such as Hostapeperm Rubin D3B LP2615, IrgazinDPP Rubin TR.

Formula (Z)

Formula (W)

Formula (V)

The organic pigment that can share, routine specifically as perylene, perylene ketone, quinoline a word used for translation ketone, quinoline a word used for translation ketone quinone, anthraquinone, three benzopyrene diketone, benzimidazolone, disazo condensation thing, bisdiazo, azo, indanthrene, phthalocyanine, triaryl carbonium, dioxazine, amino anthraquinones, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or their potpourri.

More particularly, C.I. paratonere 190 (C.I. sequence number 71140) is arranged, C.I. paratonere 224 (C.I. sequence number 71127), C.I. pigment violet 29 (pigment such as compound such as perylene such as C.I. sequence number 71129) Deng, C.I. pigment orange 43 (C.I. sequence number 71105), or C.I. paratonere 194 (C.I. sequence number 71100) perylene ketonic compound pigment, C.I. pigment violet 19 (C.I. sequence number 73900), C.I. pigment violet 42, C.I. pigment 122 (C.I. sequence number 73915), C.I. paratonere 192, C.I. paratonere 202 (C.I. sequence number 73907), C.I. Pigment Red 207 (C.I. sequence number 73900,73906), or C.I. paratonere 209 quinoline a word used for translation ketonic compound pigment such as (C.I. sequence numbers 73905), C.I. paratonere 206 (C.I. sequence number 73900/73920), C.I. pigment orange 48 (C.I. sequence number 73900/73920), or C.I. pigment orange 49 quinoline a word used for translation ketone naphtoquinone compounds pigment such as (C.I. sequence numbers 73900/73920), C.I. pigment yellow 147 anthraquinone compounds pigment such as (C.I. sequence numbers 60645), C.I. paratonere 168 three benzopyrene dione compounds pigment such as (C.I. sequence numbers 59300), C.I. pigment brown 25 (C.I. sequence number 12510), C.I. pigment violet 32 (C.I. sequence number 12517), C.I. pigment yellow 180 (C.I. sequence number 21290), C.I. pigment yellow 181 (C.I. sequence number 11777), C.I. pigment orange 62 (C.I. sequence number 11775), or C.I. paratonere 185 benzimidazolone compound pigment such as (C.I. sequence numbers 12516), C.I. pigment yellow 93 (C.I. sequence number 20710), C.I. pigment yellow 94 (C.I. sequence number 20038), C.I. pigment yellow 95 (C.I. sequence number 20034), C.I. pigment Yellow 12 8 (C.I. sequence number 20037), C.I. pigment yellow 166 (C.I. sequence number 20035), C.I. pigment orange 34 (C.I. sequence number 21115), C.I. pigment orange 13 (C.I. sequence number 21110), C.I. pigment orange 31 (C.I. sequence number 20050), C.I. paratonere 144 (C.I. sequence number 20735), C.I. paratonere 166 (C.I. sequence number 20730), C.I. paratonere 220 (C.I. sequence number 20055), C.I. paratonere 221 (C.I. sequence number 20065), C.I. paratonere 242 (C.I. sequence number 20067), C.I. paratonere 248, C.I. paratonere 262, or C.I. pigment brown 23 disazo condensation compound pigment such as (C.I. sequence numbers 20060), C.I. pigment yellow 13 (C.I. sequence number 21100), C.I. pigment yellow 83 (C.I. sequence number 21108), or C.I. pigment yellow 188 bis-azo compound pigment such as (C.I. sequence numbers 21094), C.I. paratonere 187 (C.I. sequence number 12486), C.I. paratonere 170 (C.I. sequence number 12475), C.I. pigment yellow 74 (C.I. sequence number 11714), C.I. pigment yellow 150 (C.I. sequence number 48545), C.I. pigment red 48 (C.I. sequence number 15865), C.I. paratonere 53 (C.I. sequence number 15585), C.I. pigment orange 64 (C.I. sequence number 12760), or C.I. paratonere 247 azo-compound pigment such as (C.I. sequence numbers 15915), C.I. pigment blue 60 indanthrene compound pigment such as (C.I. sequence numbers 69800), C.I. pigment Green 7 (C.I. sequence number 74260), C.I. pigment green 36 (C.I. sequence number 74265), C.I. naphthol green 37 (C.I. sequence number 74255), C.I. pigment blue 16 (C.I. sequence number 74100), C.I. alizarol saphirol 75 (C.I. sequence number 74160:2), C.I. pigment blue 15: 6 (C.I. sequence numbers 74160), or C.I. pigment blue 15: 3 phthalocyanine compound pigment such as (C.I. sequence numbers 74160), C.I. alizarol saphirol 56 (C.I. sequence number 42800), or C.I. pigment Blue-61 triaryl carbonium compound pigment such as (C.I. sequence number 42765:1), C.I. pigment Violet 23 (C.I. sequence number 51319), or C.I. pigment violet 37 (C.I. sequence number 51345) dioxazine compound pigment, C.I. paratonere 177 amino anthraquinones compound pigment such as (C.I. sequence numbers 65300), C.I. pigment Red 88 thioindigo compound pigment such as (C.I. sequence numbers 73312), C.I. pigment yellow 13 9 (C.I. sequence number 56298), C.I. pigment orange 66 isoindoline compounds pigment such as (C.I. sequence numbers 48210), C.I. pigment yellow 109 (C.I. sequence number 56284), C.I. pigment yellow 185 (C.I. sequence number 56290), or C.I. pigment orange 61 isoindoline ketonic compound pigment such as (C.I. sequence numbers 11295), C.I. pigment orange 40 (C.I. sequence number 59700), or C.I. pigment red 21 6 pyranthrone compound pigment such as (C.I. sequence numbers 59710), C.I. pigment yellow 13 8 pigment such as ketone such as phthalein such as promise such as quinoline such as grade, or C.I. pigment violet 31 isoviolanthrone compound pigment such as (C.I. sequence numbers 60010).

Among the present invention, the organic pigment more than 2 kinds or the solid solution of organic pigment can be used in combination, also can with common dye combinations after use.

With respect to whole solid content amounts, the content of the organic pigment in the color filter of the present invention in the dyed layer is preferably 10～70 quality %, 30～60 quality % more preferably.

The dispersion thing that forms the described dyed layer (pixel) of color filter of the present invention is preferably, containing described organic pigment, having in the pigment dispersing thing of the monomer of polymerizable group or oligomer and water-soluble polymers, make the polymerizing curable thing that generates after described polymerizable monomer or the oligomer polyreaction.Here the pigment dispersing thing that preferably in the pigment dispersing thing, also contains cementing agent, polymerization initiator or polymerization initiator system.

Above-mentioned monomer or oligomer with polymerizable group is preferably the ethylenical unsaturated double bonds that has more than 2, and can carry out the monomer or the oligomer of addition polymerization by illumination.As this monomer or oligomer, can enumerate and have at least one ethylenically unsaturated group that can carry out addition polymerization, the boiling point under the normal pressure in the molecule at the compound more than 100 ℃.As its example, can enumerate monofunctional acrylate or simple function methacrylates such as dipentaerythritol six (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; 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 (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) isocyanuric acid ester, three (acrylyl oxy-ethyl) cyanurate, glycerine three (methyl) acrylate; Polyfunctional alcohol such as trimethylolpropane or glycerine goes up polyfunctional acrylic ester or the multifunctional methacrylates such as material that forms through (methyl) acroleic acid esterification again behind addition of ethylene oxide or the epoxypropane.In addition, the general formula (1) that can also enumerate as Japanese kokai publication hei 10-62986 communique reaches those compounds that form through (methyl) acroleic acid esterification again of record in (2) as suitable material behind addition of ethylene oxide on the polyfunctional alcohol or epoxypropane.

In addition, also can enumerate Japanese Patent Publication 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; Polyfunctional acrylic ester or methacrylates such as epoxy acrylate class as 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.

In addition, can also enumerate the suitable material of putting down in writing in the Japanese kokai publication hei 11-133600 communique of " polymerizable compound B " conduct.

These polymerizable monomers or oligomer, preferred molecular weight are 200～1000, can use separately, or mix more than 2 kinds and use.

In the color filter of the present invention, the content of described polymerizable monomer or oligomer does not limit especially, and generally with respect to whole solid contents, the content in dyed layer is generally 5～50 quality %, is preferably 10～40 quality %.If should measure too much, then be difficult to control development, can on manufacturing adaptability, have problems.If very few, the curing power deficiency when then exposing.

The solubleness of the pure water of water-soluble polymers with respect to 25 ℃ is preferably more than and equals 100 quality %.And preferably, be difficult to color filter is exerted an influence, is neutral under the state of aqueous solution.Particularly, can use synthetic macromolecular compound and their multipolymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyacrylamide, polyglycol, polyethylene oxide.In these macromolecular compounds, special preferably polyethylene pyrrolidone.That these water-soluble polymerss can only use is a kind of, also can be used in combination more than 2 kinds.

The molecular weight of described water-soluble polymers does not limit especially, and its number-average molecular weight Mn is preferably 1,000～2, and 000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, be preferably 10,000～100,000 especially.

With respect to whole solid content amounts, the content of water-soluble polymers be preferably more than equal 0.1 quality %, more preferably more than or equal to 1 quality %, more preferably more than or equal to 3 quality %, be preferably more than and equal 5 quality % especially.

As cementing agent, preferably have the cementing agent of acidic-group, when preparation ink-jet ink or photosensitive composition, also can add described cementing agent.When making described pigment dispersing thing, perhaps when forming pigment particle described later, also preferably add described cementing agent.Can and be added in organic pigment solution and add described cementing agent in the poor solvent that behind the organic pigment solution pigment particle is produced or add described cementing agent among the side therein.When forming pigment particle, add described cementing agent in the perhaps also preferred other system.

As cementing agent, preferably, has the alkali-soluble polymer of hydroxy-acid group or carboxylate groups isopolarity group on the side chain.Maleic acid of methacrylic acid copolymer described in Japanese kokai publication sho 59-44615 communique, Japanese Patent Publication 54-34327 communique, Japanese Patent Publication 58-12577 communique, Japanese Patent Publication 54-25957 communique, Japanese kokai publication sho 59-53836 communique, the Japanese kokai publication sho 59-71048 communique, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification etc. is for example arranged.Also for example there is side chain to have the cellulose derivative of hydroxy-acid group or carboxylate groups etc.In addition, also can use polymkeric substance with hydroxyl and the compound after the cyclic acid anhydride addition reaction.More preferred example, U.S. Patent No. 4 is for example arranged, the multiple copolymer of (methyl) acrylic acid benzyl ester described in 139, No. 391 the instructions and (methyl) acrylic acid multipolymer or (methyl) acrylic acid benzyl ester and (methyl) acrylic acid and other monomer.These binder polymers with polar group can use separately, also can use with the form of the composition that share with common polymkeric substance with film forming, with respect to 100 mass parts of pigment particle, its consumption is generally 10～200 mass parts, is preferably 25～100 mass parts.

In addition, in order to improve cross-linking efficiency, also can have polymerizable group on side chain, UV curable resin or heat-curing resin etc. also are useful.Though show the example that some contain the polymkeric substance of polymerizable group below, have more than and be defined in these examples, get final product so long as contain the compound of alkali solubility groups such as COOH base, OH base, ammonium and carbon-to-carbon unsaturated bond.Can use such compound: make contain the OH base compound for example acrylic acid 2-hydroxy methacrylate, contain the COOH base compound as methacrylic acid and can with the acrylic compounds of their copolymerizations or the formed multipolymer of monomers such as compound that contains vinyl with have the epoxide ring that can react and the compound reaction back resulting compound of compound as glycidyl acrylate of carbon-to-carbon unsaturated bond group etc. with the OH base.Can react with OH, except that epoxide ring, can also use acid anhydrides, have isocyanate group compound, have the compound of acryloyl group.In addition, also can use: the disclosed resulting compound of compound and the reaction of the unsaturated carboxylic acid acrylic acid back with epoxide ring reacts the resulting reactant in back with saturated or unsaturated multi-anhydride again in Japanese kokai publication hei 6-102669 communique, Japanese kokai publication hei 6-1938 communique.The compound that has such alkali solubility group of COOH and carbon-to-carbon unsaturated group simultaneously, ダイヤ Na one Le NR series (manufacturing of Rayon Co., Ltd. of Mitsubishi) is for example arranged, Photomer 6173 (the polyurethane acroleic acid oligomer that contains the COOH base, Diamond Shamrock company makes), PVC スコ one ト R-264, KS レジスト 106 (being Osaka Organic Chemical Industry Co., Ltd. makes), サイ Network ロマ one P series, プラ Network セ Le CF200 series (being Daicel chemical industry Co., Ltd. makes), Ebecry 13800 (manufacturing of Daicel ユ one シ one PVC one Co., Ltd.) etc.

As resin glue, can use the organic high molecular polymer that on the part of side chain, has water miscible atomic group.Above-mentioned resin glue is for to have the wire organic high molecular polymer of compatibility with monomer, and preferably dissolves in organic solvent and have alkali solubility (being preferably those that can develop with weak base aqueous solution).As above-mentioned alkali soluble resins, there is side chain to have the polymkeric substance of carboxylic acid, for example such as Japanese kokai publication sho 59-44615 communique, Japanese Patent Publication 54-34327 communique, Japanese Patent Publication 58-12577 communique, Japanese Patent Publication 54-25957 communique, Japanese kokai publication sho 59-53836 communique, the methacrylate copolymer of being put down in writing in the Japanese kokai publication sho 59-71048 communique, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, maleic acid, the maleic acids of partial esterification etc. also have the acid cellulose derivant that has carboxylic acid equally on side chain in addition.In addition, as above-mentioned alkali soluble resins, it also is useful having the material that forms behind the addition acid anhydrides on the polymkeric substance of hydroxyl.Specifically, (methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer in preferred especially these materials, and the multiple copolymer of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid and other monomer.As above-mentioned alkali soluble resins, can use at least by at least a sour composition monomer of selecting in (i) maleic anhydride (MAA), acrylic acid (AA) and the fumaric acid (FA) and (ii) alkyl polyoxyethylene (methyl) acrylate and the (iii) formed multipolymer of (methyl) acrylic acid benzyl ester (following be called sometimes " copolymer A ").

As the composition of described copolymer A, (i) sour composition monomer, (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) _n: CH ₃(OC ₂H ₄) _nOCOC (R)=CH ₂) and (iii) the composition mass ratio of (methyl) acrylic acid benzyl ester (Bz (M) A) be preferably 10～25/5～25/50～85, more preferably 15～20/5～20/60～80.In addition, described polymkeric substance is preferably 3,000～50,000, more preferably 5,000～30,000 by the quality mean molecular weight (Mw) through polystyrene conversion that GPC measured.

If (i) the composition mass ratio of sour composition monomer is positioned at above-mentioned scope, alkali solubility and the dissolubility in solvent just can not reduce.If (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) _n: CH ₃(OC ₂H ₄) _nOCOC (R)=CH ₂) the composition mass ratio be positioned at above-mentioned scope, composition liquid on substrate is easy to sprawl, and the dispersiveness of colorant can not descend yet, and can reach effect of the present invention effectively.If (iii) the composition mass ratio of (methyl) acrylic acid benzyl ester (Bz (M) A) is positioned at above-mentioned scope, the dispersion stabilization of colorant, colorant dissolubility and the alkali of the coated film suitable property of developing in composition can not descend.

(ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) _n: CH ₃(OC ₂H ₄) _nOCOC (R)=CH ₂) in the repetitive number n of polyoxyethylene (EO) n be preferably 2～1 5, more preferably 2～10, be preferably 4～10 especially.Described repetitive number n is in this scope the time, after developing with alkaline developer, can not produce the development residue, in the time of can preventing composition as coating liquid owing to mobilely reduce the coating non-uniform phenomenon that causes, also can prevent the performance decline that the homogeneity of coated film thickness descends and saves coating liquid this respect.

These binder polymers with polar group can use separately, and also the form of the composition that can share with the polymkeric substance with common tool film forming is used.With respect to 100 mass parts of pigment particle, the addition of cementing agent is generally 10～200 mass parts, is preferably 25～100 mass parts.

When described cementing agent is macromolecular compound, the number of the acidic-group in this macromolecular compound does not limit especially, if the repetitive number that is contained in 1 molecule is 100, the repetitive with acidic-group is preferably 5～100, more preferably 10～100.And, with regard to (1) by the repetitive of compound deriving and (2) with carboxyl with regard to the polymerization ratio of the repetitive of compound deriving with carboxylic acid ester groups, the mole % of repetitive (1) is preferably 5～40, the mole % of repetitive (2) is preferably 40～90, and the mole % of repetitive (1) or repetitive (2) repetitive in addition is preferably below 25.In addition, the molecular weight as the macromolecular compound of the alkali solubility cementing agent with acidic-group is preferably 3000～1000000, more preferably 4000～200000, is preferably 5000～80000 especially.

In the color filter of the present invention, the content of the cementing agent in the dyed layer does not limit especially, with respect to whole solid content amounts, is generally 15～50 quality %, is preferably 20～45 quality %.Surpass this amount, the viscosity of composition is too high, is making on the adaptability and can have problems.Be less than this amount, when forming coated film, can have problems.

Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system are (in the present invention, the Photoepolymerizationinitiater initiater system is meant to be combined by multiple compound and realizes that photopolymerization causes the potpourri of function), can enumerate disclosed vicinal polyketaldonyl compound in No. 2367660 instructions of United States Patent (USP), the acyloin ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series acyloin compound that the α that puts down in writing in No. 2722512 instructions of United States Patent (USP)-hydrocarbon replaces, 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 dipolymer of putting down in writing in No. 3549367 instructions of United States Patent (USP) and to the combination of amino ketones, benzothiazole compound of putting down in writing in the Japanese Patent Publication 51-48516 communique and trihalomethyl-s-triaizine compounds, trihalomethyl-triaizine compounds of putting down in writing in No. 4239850 instructions of United States Patent (USP), the San halogen Jia oxadiazole compound of putting down in writing in No. 4212976 instructions of United States Patent (USP) etc.Preferred especially trihalomethyl-s-triazine, San halogen Jia oxadiazole and triarylimidazoles dipolymer.

In addition; can also enumerate " the polymerization initiator C " that put down in writing in the Japanese kokai publication hei 11-133600 communique; and as the 1-phenyl-1 of oximes; 2-propanedione-2-(adjacent carbethoxyl group) oxime, O-benzoyl-4 '-(thiophenyl) benzoyl-hexyl-ketoxime, 2; 4,6-trimethylphenyl carbonyl-diphenylphosphine acyl-oxygen, hexafluorophosphoric acid-trialkyl Ben phosphonium salt etc. are as preferred material.

These Photoepolymerizationinitiater initiaters or Photoepolymerizationinitiater initiater system can be used separately, also can mix more than 2 kinds and use, and especially preferably use more than 2 kinds.If use at least 2 kinds of Photoepolymerizationinitiater initiaters, then can reduce the demonstration non-uniform phenomenon in the display characteristic especially.

In the color filter of the present invention, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system does not limit especially, with respect to the amount of whole solid contents, is generally 0.5～20 quality % in the dyed layer, is preferably 1～15 quality %.If should measure too much, then susceptibility is too high, is difficult to control.If very few, then exposure sensitivity is low excessively.

Except that mentioned component, in addition can also be with an organic solvent.To as representative examples of organic, be not particularly limited, can enumerate the ester class, for example ethyl acetate, n-butyl acetate, isobutyl acetate, the formic acid pentyl ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the hydroxacetic acid methyl esters, the hydroxacetic acid ethyl ester, the hydroxacetic acid butyl ester, Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the ethoxy methyl acetate, the ethoxy ethyl acetate, the 3-hydroxy methyl propionate, 3-hydracrylic acid alkyl esters such as 3-hydracrylic acid ethyl ester; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, the 2-beta-hydroxymethyl butyrate, 2-3-hydroxyethyl butyrate etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methyl cellosolve, acetic acid ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate etc.; Ketone, for example MEK, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone etc.; Arene, for example toluene, dimethylbenzene etc.In these solvents, preferably use 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetic acid ethyl cellosolve, ethyl lactate, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate etc. as the solvent among the present invention.These solvents can use separately or be used in combination more than 2 kinds.

In addition, can use boiling point in case of necessity is 180 ℃～250 ℃ solvent.As these high boiling solvents, can the following material of illustration.Diethylene glycol single-butyl ether, TC acetate, TC, 3,5,5-trimethyl-2-cyclohexene-1-ketone, butyl lactate, DPGME acetate, propylene glycol monomethyl ether acetate, PGDA, propylene glycol n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxyl-3-methyl butyl acetate, gamma-butyrolacton, tripropylene glycol Methylethyl acetate, dipropylene glycol n-butyl acetate, propylene glycol phenyl ether acetate, 1,3 butylene glycol diacetate.

The content of solvent does not limit especially, and the amount with respect to whole solid contents in the dyed layer of color filter is preferably 10～95 quality %.

In the color filter that in the past uses, in order to realize high color purity, need make each color of pixel enriching, people recognize and do the following problem that exists like this that promptly the membrane thickness unevenness of pixel causes color inhomogeneous.Therefore, need improve the direct Thickness Variation that influences the film thickness of pixel.

For color filter of the present invention, from controlling uniform thickness, effectively preventing from the uneven viewpoint of color that Thickness Variation causes to contain suitable surfactant in the preferred ink-jet ink for color filter.

As above-mentioned surfactant, can enumerate TOHKEMY 2003-337424 communique, spy and open in the flat 11-133600 communique disclosed surfactant as the surfactant that is fit to.The content of the surfactant in the dyed layer does not limit especially, is preferably below the 5 quality % with respect to whole solid content amounts.

Preferably contain thermal polymerization in the color filter of the present invention and prevent agent.Prevent the example of agent as this thermal polymerization, can enumerate quinhydrones, Hydroquinone monomethylether, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-sulphur two (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, phenothiazine etc.Thermal polymerization in the dyed layer prevents that the content of agent from not limiting especially, is preferably below the 1 quality %.

In case of necessity, can contain ultraviolet light absorber in the color filter of the present invention.As ultraviolet light absorber, the compound of in Japanese kokai publication hei 5-72724 communique, putting down in writing, also can enumerate salicylate class, benzophenone, benzotriazole, cyanoacrylate, nickel chelate class, hindered amines etc.

Specifically, can enumerate the salicylic acid phenylester, 4-tert-butyl-phenyl salicylate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, 4-tert-butyl-phenyl salicylate, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-cyano group-3, the 3-diphenyl-ethyl acrylate, 2,2 '-hydroxyl-4-methoxy benzophenone, nickel dibutyl dithiocarbamate, two (2,2,6,6-tetramethyl-4-pyridine)-sebacate, 4-tert-butyl-phenyl salicylate, the salicylic acid phenylester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation product, succinic acid-two (2,2,6,6-tetramethyl-4-piperidyl)-ester, 2-[2-hydroxyl-3, two (α, the α-Er Jiajibianji) phenyl of 5-]-the 2H-benzotriazole, 7-{[4-chloro-6-(lignocaine)-5-triazine-2-yl] amino }-3-phenyl cumarin etc.The content of the ultraviolet light absorber in the dyed layer does not limit especially, with respect to whole solid content amounts, is preferably below the 5 quality %.

In the color filter of the present invention, described pigment dispersing thing is suitable as ink-jet ink when pixel forms.Details about ink-jet ink used in the color filter of the present invention will be described below.

In addition, when above-mentioned pigment dispersing thing formed coated film as photosensitive composition, its thickness can suitably determine, but was preferably 0.5～5.0 μ m, more preferably 1.0～3.0 μ m.For the coated film that forms with this photosensitive composition, make wherein contained polymerizable monomer or oligomer carry out the polymeric membrane that polymerization forms photosensitive composition, can make the color filter (, hereinafter stating) that contains this film about the making of color filter.The polymerization of polymerizable monomer or polyreactive oligomers can be undertaken by Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system are worked.

In addition, though above-mentioned coated film can be by forming with common coating process coating and dry photosensitive composition, the slit-shaped nozzle that preferably adopts hydrojet portion to have slit-shaped apertures is coated with.Specifically, preferably using TOHKEMY 2004-89851 communique, spy to open 2004-17043 communique, spy opens 2003-170098 communique, spy and opens 2003-164787 communique, spy and open 2003-10767 communique, spy and drive slit-shaped nozzle and the slot coated device that 2002-79163 communique, spy are opened record in the 2001-310147 communique etc.

As the method for photosensitive composition being coated on the substrate, from can all even aspect that is coated with the film of 1～3 μ m accurately, rotary coating be excellent, and this method has obtained extensive widespread usage in color filter is made.But, be accompanied by the maximization and the batch process of liquid crystal indicator in recent years, to make efficient and save cost in order further to improve, in the making of color filter, adopting than the rotation coating to be more suitable in the slot coated of carrying out the coating of wide cut large tracts of land substrate.In addition, from saving the viewpoint of liquid, slot coated is also excellent than the rotation coating, can be filmed uniformly with coating liquid measure still less.Herein, substrate is preferably transparent substrates, can use glass plates such as the soda-lime glass plate that has silicon oxide film on the surface, low-expansion glass, quartz glass plate.In addition, also can use resin moldings such as polyethylene terephthalate, Triafol T, polystyrene, polycarbonate.

Slot coated is a kind of like this coating process, promptly, making front end have width is that the gap of tens of microns slit (gap) and length dispense tip corresponding with the coating width of rectangular substrate and substrate remains tens of～hundreds of microns, make substrate and dispense tip keep constant relative velocity simultaneously, will be coated on the substrate by the coating fluid that slit provides by predetermined coating weight.This slot coated have (1) compare with rotary coating liquid loss less, (2) no coating fluid disperses, therefore reduced the liquid that can not that disperses in cleaning treatment, (3) and sneaked into the time that coated film, (4) rotates beginning and stop again, therefore shortened and produce interval, (5) easily to advantages such as large-sized substrate are coated with.Owing to have these advantages, slot coated is suitable for the making of the liquid crystal indicator of large-scale picture with color filter, also is expected to become favourable coating process with regard to the minimizing of coating weight.

Because slot coated can form area more than the big coated film of rotary coating, therefore when the slit outlet from broadness sprays coating fluid, must make the relative velocity that keeps between spreader and the coated article to a certain degree.Therefore, the coating fluid that uses in the slot coated mode requires to have good flowability.In addition, in slot coated, the various conditions that especially require to be provided to the coating fluid on the substrate from the slit of dispense tip keep constant at whole coating width.If liquid rerum natura deficiencies such as the flowability of coating fluid and viscoelastic property then can produce following problem, it is even that crawling promptly takes place easily, is difficult to keep constant coating thickness in the coating width direction, can not form uniform coated film.

Because above situation in order there not to be uneven even coated film, has been carried out flowability and viscoelastic property that a large amount of trials improve coating fluid.But, as mentioned above, though proposed to reduce the molecular weight of polymkeric substance, or selection is to the polymkeric substance of the dissolubility excellence of solvent, or select all kinds of solvents in order to control velocity of evaporation, or use means such as surfactant, but do not have a kind of means can fully improve above-mentioned variety of issue.

Photosensitive resin transfer material forms by using above-mentioned photosensitive composition to be arranged to photoresist, and preferably with the photosensitive resin transfer material of putting down in writing in the Japanese kokai publication hei 5-72724 communique, promptly the monolithic devices film forms.The example of this monolithic devices film formation can be enumerated and carry out laminated in this order interim stilt/thermoplastic resin/middle layer/photo-sensitive resin/diaphragm and structure that obtain as an illustration.

As interim stilt, has flexible also can not produce remarkable distortion, contraction or elongation under pressurization or heating and pressurizing material even must be.As the example of this interim stilt, can enumerate polyethylene terephthalate film, three cellulose acetate membrane, polystyrene film, polycarbonate membrane etc., wherein preferred especially biaxial stretch-formed polyethylene terephthalate film.

As the composition that uses in the thermoplastic resin, the organic polymer material of putting down in writing in the preferred Japanese kokai publication hei 5-72724 communique, be to select in about organic polymer material below 80 ℃ especially preferably from the softening point that records by Wei Ka-Vicat method (specifically, being the method for measuring the polymkeric substance softening point according to U.S. material test method(s) ASTMD 1235).Specifically, can enumerate tygon, polyolefin such as polypropylene, the ethylene copolymer that ethene and vinyl acetate or its are saponified etc., ethene and acrylate or its are saponified, Polyvinylchloride, vinyl chloride and vinyl acetate and saponified etc. vinyl chloride copolymer thereof, Vingon, polyvinylidene chloride copolymer, polystyrene, the styrol copolymer that styrene and (methyl) acrylate or its are saponified etc., polyvinyl toluene, the vinyl toluene copolymer that vinyltoluene and (methyl) acrylate or its are saponified etc., poly-(methyl) acrylate, (methyl) acrylate copolymer that (methyl) butyl acrylate and vinyl acetate etc. form, vinyl acetate copolymerized nylon, copolymer nylon, N-alkoxy methyl nylon, the organic polymers such as polyamide of N-dimethylamino nylon and so on.

For photosensitive resin transfer material, when after coating, preserving,, the middle layer is set preferably in order to prevent the mixing of composition in order when being coated with a plurality of coating layer, to reach.As this middle layer, the preferred oxygen barrier film that uses conduct " separating layer " in the Japanese kokai publication hei 5-72724 communique and put down in writing with the function that stops oxygen, in this case, the susceptibility during exposure rises, reduce the time load of exposure machine, improved throughput rate.

As the oxygen barrier film, the lower oxygen permeability of preferred demonstration can be dispersed or dissolved in the material in water or the aqueous alkali, can suitably select from common material.Wherein, the combination of the special pure and mild polyvinylpyrrolidone of preferably polyethylene.

The thin diaphragm of pollution when preferably on photo-sensitive resin, being provided for protecting it to avoid storing and damage.Diaphragm can be to be made of or materials similar identical with interim stilt, but must separate with photo-sensitive resin easily.As the material of diaphragm, for example organosilicon paper, polyolefin or polytetrafluoroethylsheet sheet suit.

Photosensitive resin transfer material can be made in the following manner, promptly, coating is dissolved and the coating fluid (thermoplastic resin coating fluid) of formation the adjuvant of thermoplastic resin on interim stilt, dry then, thermoplastic resin is set thus, the intermediate layer material solution that coating is made of the solvent of heat of solution plastic resin layer not on thermoplastic resin then, and carry out drying, adopt the solvent that does not dissolve the middle layer to be coated with and drying then, thereby photo-sensitive resin is set.

In addition, also can make in the following manner, that is, prepare on above-mentioned interim stilt, to be provided with the sheet material in thermoplastic resin and middle layer, and the sheet material that on diaphragm, is provided with photo-sensitive resin, carry out bonding mutually according to the mode that the middle layer is contacted with photo-sensitive resin; Also have, prepare on above-mentioned interim stilt, to be provided with the sheet material of thermoplastic resin, and the sheet material that on diaphragm, is provided with photo-sensitive resin and middle layer, carry out bonding mutually according to the mode that thermoplastic resin and middle layer are engaged.

In photosensitive resin transfer material, the thickness of photo-sensitive resin is preferably 1.0～5.0 μ m, and more preferably 1.0～4.0 μ m are preferably 1.0～3.0 μ m especially.In addition, though be not particularly limited, preferred thickness of each layer as other, preferred usually interim stilt is 15～100 μ m, and thermoplastic resin is 2～30 μ m, and the middle layer is 0.5～3.0 μ m, and diaphragm is 4～40 μ m.

In addition, the coating in the above-mentioned method for making can utilize common apparatus for coating etc. to carry out, but preferred the employing uses the apparatus for coating (slot coated device) of slit-shaped nozzle to be coated with.The preferred object lessons of slot coated device etc. are same as described above.

According to purposes, color filter of the present invention can only have single color, perhaps has red, blue, green 3 kinds of different colors.Pattern of dyed layer on the substrate (pixel) and forming method thereof is not limited especially.

Color filter of the present invention can be used as the color filter of contrast excellence and uses.In the present invention, contrast is illustrated between two polaroids, the ratio of the light transmission capacity the when light transmission capacity when polarizing axis is parallel is vertical with polarizing axis (referring to " nineteen ninety the 7th the color reversion glory learn コ Application Off アレ Application ス; 512 colour specifications 10.4 " サイズ TFT-LCD is with カラ-Off イ Le , plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).

Light and shade difference when the contrast height of color filter is meant and makes up with liquid crystal can become big, and in order to replace CRT with LCD, this is very important performance.

When color filter of the present invention is used as TV, preferably under the F10 light source, all the monochromatic colourities of red (R), green (G) and blue (B) and following table record value (below, be called " standard colorimetric " in the present invention.) poor (Δ E) in 5, more preferably in 3, in 2.

	x	y	Y
	x	y	Y	R G B	0.656 0.293 0.146	0.336 0.634 0.088	21.4 52.1 6.90

Colourity among the present invention is to utilize microscope spectrophotometer (オリ Application パス optics society make, OSP100 or 200) to measure, and calculates as the result of F10 light source downward view 2 degree, represents with the xyY value of xyz color specification system.In addition, with the difference of target colourity with La ^*b ^*The aberration of color specification system is represented.

The methods such as method that form the operation that photo-sensitive resin, exposure back develop on substrate of number of times that can be by repeating to be equivalent to number of color are made color filter of the present invention.In addition, as required, also can form the structure of distinguishing the border with black matrix.

In above-mentioned manufacture method, as the method that on substrate, forms above-mentioned photo-sensitive resin, there be (a) to adopt method that applying device commonly used etc. will above-mentioned each photosensitive composition applies for example and (b) utilize above-mentioned photosensitive resin transfer material, the method for pasting by lamination etc.

When making color filter of the present invention, the coating of photosensitive composition can be adopted applying device commonly used, and wherein particularly aforesaid slit coating machine also is to be fit to use.The same in the preferred concrete example of slit coating machine etc. and the aforementioned content.When forming photo-sensitive resin by coating, film thickness be preferably 1.0～3.0 μ m, more preferably 1.0～2.5 μ m, be preferably 1.5～2.5 μ m especially.

Use described photosensitive resin transfer material to form membranaceous and photo-sensitive resin that obtain, use roller or dull and stereotyped pressing or heating to be pressed together on the substrate described later, thereby paste through heating and/or pressurization.Specifically, can enumerate Japanese kokai publication hei 7-110575 communique, spy and open that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy opens laminating machine and the laminating method of putting down in writing in the 2002-148794 communique, but from the few viewpoint of impurity, the special method of putting down in writing in the flat 7-110575 communique of opening of preferred employing.

In the color filter of the present invention, when forming photo-sensitive resin, can the oxygen barrier film be set further on this photo-sensitive resin, can improve exposure sensitivity thus by the colored coating photosensitive polymer combination.As this oxygen barrier film, can enumerate the film identical with the film that has illustrated.In addition, though do not do special qualification, the thickness of oxygen barrier film is preferably 0.5～3.0 μ m usually.

Above the photo-sensitive resin that forms on the above-mentioned substrate, be provided with predetermined mask, see through this mask, thermoplastic resin and middle layer then, top exposure from mask, then develop with developer solution, such operation of the number of times by repeating to be equivalent to number of color just can obtain color filter.

Herein,, can suitably select to use, get final product so long as can penetrate the light (for example 365nm, 405nm etc.) of the wavelength coverage that makes photo-sensitive resin curing as the light source of described exposure.Particularly, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, metal halide lamp etc. are for example arranged.Exposure is generally 5～200mJ/cm ²About, be preferably 10～100mJ/cm ²About.

To the not restriction especially of described developer solution, can use the developer solutions commonly used such as developer solution described in Japanese kokai publication hei 5-72724 communique.In addition, the preferred use carried out the developer solution that lysotype is developed to photo-sensitive resin, and the compound and its concentration that for example preferably contain pKa=7～13 are the developer solution of 0.05～5mol/L, can also add a small amount of and the miscible organic solvent of water in this developer solution.

The organic solvent miscible with water has methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, MEK, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone etc. for example.The concentration of this organic solvent is preferably 0.1 quality %～30 quality %.

In addition, in above-mentioned developer solution, can also add surfactant commonly used.Surfactant concentrations is preferably 0.01 quality %～10 quality %.

About the mode of developing, can use to stir and develop, spray development, spray and methods such as rotation development, immersion development.

Above-mentioned spray is developed herein and describe.On the photo-sensitive resin after the exposure,, remove uncured part by the mode spray developing liquid of spray.In addition, preferably, before development, spray the akaline liquid low, to remove thermoplastic resin, middle layer to the dissolubility of photo-sensitive resin in modes such as sprays.In addition also preferably, after development,, use the brush wiping, remove the development residue with the mode jet cleaning agent of spray.

The temperature of developer solution is preferably 20 ℃～40 ℃, and the pH of developer solution is preferably 8～13.

When making color filter of the present invention, as described in Japanese kokai publication hei 11-248921 communique, No. 3255107 communiques of Jap.P., the stacked matrix that forms of photosensitive composition of color filter will be formed, on this matrix, form transparency electrode, the protuberance layer that division alignment is used is laminated on the established dottle pin again, considers that from the aspect that reduces cost this is preferred.

Photosensitive composition is applied the back when stacked in turn, because the levelling (leveling) of coating liquid, along with stacked, the thickness attenuation of film.Therefore, preferably,, again that division alignment is stacked with projection earlier with K (deceiving), R, G, the colour superimposition of B4 kind.On the other hand, use when having the transfer materials of thermoplastic resin, keep certain in order to make thickness, overlapping color is preferably 3 looks or 2 looks.

Photo-sensitive resin deforms and keeps the aspect of certain thickness to consider during lamination after preventing stacked transfer materials, the size of above-mentioned matrix be preferably 25 μ m * 25 μ m above, be preferably 30 μ m * more than the 30 μ m especially.

In color filter of the present invention, contain the organic pigment particulate in the pixel (dyed layer), this particulate be by will in good solvent, dissolve organic pigment solution that organic pigment forms and for above-mentioned good solvent have compatibility, for organic pigment be poor solvent solvent (below, sometimes also this solvent is called by " poor solvent of organic pigment ", or abbreviate " poor solvent " etc. as) mix and generate (below, also this method is called " particulate deposition method " sometimes).And the combination of above-mentioned poor solvent and good solvent must have sufficient organic pigment poor solubility, can select the preferred combination that is consistent with pigment, as long as but can make this operation become possible any combination all can.

There is no particular limitation to the poor solvent of organic pigment, if can with miscible or even mixing of good solvent of dissolving organic pigment.As the poor solvent of organic pigment, the solubleness of preferred organic pigment is below the 0.02 quality %, more preferably those below the 0.01 quality %.The solubleness of organic pigment in poor solvent does not have specific lower limit, if but consider normally used organic pigment, then be actually more than the 0.000001 quality %.This solubleness also can be the solubleness of carrying out in the presence of acid or the alkali under the dissolving situation having.In addition, as the compatibility or the even Combination of good solvent and poor solvent, preferred good solvent is more than the 30 quality % to the meltage of poor solvent, more preferably more than the 50 quality %.Good solvent does not have specific upper limit to the meltage of poor solvent, is actually with arbitrary proportion and mixes.

As poor solvent, for example (for example can enumerate aqueous solvent, water, or hydrochloric acid, sodium hydrate aqueous solution), the alcoholic compound solvent, the ketonic compound solvent, the ether compound solvent, aromatic compound solvent, the carbon disulphide solvent, the fatty compound solvent, the nitrile compound solvent, the halogen compounds solvent, the ester compounds solvent, ionic liquid, their mixed solvent etc., preferred aqueous solvent, the alcoholic compound solvent, the ketonic compound solvent, the ether compound solvent, the ester compounds solvent, or their potpourri, more preferably aqueous solvent, alcoholic compound solvent or ester compounds solvent.

As the alcoholic compound solvent, for example can enumerate methyl alcohol, ethanol, isopropyl alcohol, n-propanol, 1-methoxyl-2-propyl alcohol etc.As the ketonic compound solvent, for example can enumerate acetone, MEK, methyl isobutyl ketone, cyclohexanone.As the ether compound solvent, for example can enumerate dimethyl ether, Anaesthetie Ether, tetrahydrofuran etc.As aromatic compound solvent, for example can enumerate benzene, toluene etc.As the fatty compound solvent, for example can enumerate hexane etc.As the nitrile compound solvent, for example can enumerate acetonitrile etc.As the halogen compounds solvent, for example can enumerate methylene chloride, triclene etc.As the ester compounds solvent, for example can enumerate ethyl acetate, ethyl lactate, 2-(1-methoxyl) propyl group acetate etc.As ionic liquid, for example can enumerate 1-butyl-3-methylimidazole and PF ₆ ^-Salt etc.

There is no particular limitation to good solvent, as long as can dissolve employed organic pigment, and can be miscible with above-mentioned poor solvent or get final product even the mixing.For the dissolubility of organic pigment in good solvent, the solubleness of preferred organic pigment is more than the 0.2 quality %, more preferably more than the 0.5 quality %.The solubleness of organic pigment in good solvent does not have specific upper limit, if consider that from normally used organic pigment then this solubleness is actually below the 50 quality %.This solubleness also can be the solubleness of carrying out in the presence of acid or the alkali under the dissolving situation having.The compatibility of good solvent and poor solvent or even blended preferable range are for as mentioned above.

As good solvent, for example can preferred following solvent: aqueous solvent (for example, water, water-soluble alcohol, hydrochloric acid, or sodium hydrate aqueous solution), the alcoholic compound solvent, the amide compound solvent, the ketonic compound solvent, the ether compound solvent, aromatic compound solvent, the carbon disulphide solvent, the fatty compound solvent, the nitrile compound solvent, the sulfoxide compound solvent, the halogen compounds solvent, the ester compounds solvent, ionic liquid, their mixed solvent etc., preferred aqueous solvent, the alcoholic compound solvent, the ketonic compound solvent, the ether compound solvent, the sulfoxide compound solvent, the ester compounds solvent, the amide compound solvent, or their potpourri.Wherein, more preferably following solvent: aqueous solvent, alcoholic compound solvent, ester compounds solvent, sulfoxide compound solvent or amide compound solvent, further preferred following solvent: aqueous solvent, sulfoxide compound solvent or amide compound solvent, especially preferably contain sulfoxide compound solvent or amide compound solvent.

As the sulfoxide compound solvent, for example can enumerate dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide, sulfolane etc.As the amide compound solvent, for example can enumerate N, dinethylformamide, 1-Methyl-2-Pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-Pyrrolidone, 2-Pyrrolidone, epsilon-caprolactams, formamide, N-NMF, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, hexamethyl phosphoric triamide etc.

In addition, as the concentration that organic pigment is dissolved in the organic pigment solution that forms in the good solvent, preferably its scope is: under the condition in when dissolving organic pigment for the saturation concentration of good solvent to about 1/100 of this saturation concentration.

The preparation condition of organic pigment solution is not particularly limited, and can select normal pressure to scope critical, super critical condition.Temperature under the normal pressure is preferably-10～150 ℃, more preferably-5～130 ℃, is preferably 0～100 ℃ especially.

Herein, the solvent of enumerating as the concrete example of good solvent has identical solvent with the solvent of enumerating as poor solvent, but identical solvent is not used in combination as good solvent with as poor solvent, fastening with the pass of each organic pigment that is adopted, the solubleness of organic pigment in good solvent gets final product greatly than the solubleness of organic pigment in poor solvent, for example, their poor solubility be preferably more than equal 0.2 quality %, more preferably more than or equal to 0.5 quality %.The poor solubility of organic pigment in good solvent and poor solvent do not have the special upper limit, but considers from general employed organic material aspect, is realistic smaller or equal to 50 quality %.

In above-mentioned particulate deposition method, organic pigment can be dissolved in the good solvent equably, also preferably under acidity or alkalescence, dissolve.Usually, use the solvent that contains alkali when in adopting molecule, having the pigment of the group that can under alkali condition, dissociate, and in adopting molecule, do not have the group that can under alkali condition, dissociate and use acid flux material when having the pigment of nitrogen-atoms of a plurality of easy generation proton addition reaction.For example, quinoline a word used for translation ketonic compound pigment, Diketopyrrolo-pyrrole compounds pigment, disazo condensation compounds pigment optimization dissolve under alkali condition, and the phthalocyanine compound pigment optimization dissolves under acid condition.

Dissolving used alkali during organic pigment under alkali condition, inorganic bases such as lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide or baryta hydrate are arranged, or organic bases such as trialkylamine, diazabicyclo hendecene (DBU), metal alkoxide, but preferred inorganic base.

The amount of the alkali that uses is the amount that can make the pigment uniform dissolution, there is no particular limitation to this amount, but under the situation of using inorganic base, be 1.0～30 molar equivalents with respect to organic pigment preferably, more preferably 1.0～25 molar equivalents, more preferably 1.0～20 molar equivalents.Using under the situation of organic base, be 1.0～100 molar equivalents preferably with respect to organic pigment, more preferably 5.0～100 molar equivalents, more preferably 20～100 molar equivalents.

The used acid of dissolving organic pigment has mineral acid or organic acids such as acetic acid, trifluoroacetic acid, oxalic acid, methane-sulforic acid or trifluoromethanesulfonic acid such as sulfuric acid, hydrochloric acid or phosphoric acid under acid condition, but preferred mineral acid, special preferably sulfuric acid.

To use the amount of acid be the amount that can make the organic pigment uniform dissolution, there is no particular limitation to this amount, compares the excessive acid of using with alkali more.No matter be mineral acid or organic acid, be 3～500 molar equivalents, more preferably 10～500 molar equivalents, 30～200 molar equivalents more preferably preferably with respect to organic pigment.

Alkali or acid mix with organic solvent, when using as the good solvent of organic pigment, dissolve in order to make alkali or acid fully, can add some water or lower alcohol etc. to alkali or sour solvent with high-dissolvability in organic solvent.The amount of preferred water or lower alcohol is below the 50 quality % with respect to organic pigment solution total amount, more preferably below the 30 quality %.Specifically, can make water, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, butanols etc.

There is no particular limitation for the condition of the poor solvent when making pigment particle separate out generation, can select from normal pressure to scope subcritical, super critical condition.Temperature under the normal pressure is preferably-30～100 ℃, more preferably-10～60 ℃, is preferably 0～30 ℃ especially.The viscosity of pigment particle lye is preferably 0.5～80.0mPas, 1.0～50.0mPas more preferably.

When organic pigment solution and poor solvent mix, can mix by adding among both any, mix but preferably organic pigment is added in the poor solvent, this moment, preferred poor solvent kept stirring.Stirring rate is preferably 100～10000rpm, and more preferably 150～8000rpm is preferably 200～6000rpm especially.Can use during interpolation, also can not use equipment such as pump.In addition, can in liquid, submergence add, also can outside liquid, add, but more preferably submergence interpolation in liquid.Among the present invention, preferably, by supply pipe, in liquid, supply with continuously with pump.The internal diameter of supply pipe is preferably 0.1～200mm, 0.2～100mm more preferably.The speed of supplying with in liquid by supply pipe is preferably 1～10000ml/min, 5～5000ml/min more preferably.

The mixing ratio of organic pigment solution and poor solvent (ratio of the good solvent/poor solvent in the pigment particle lye) is preferably 1/50～2/3 by volume, and more preferably 1/40～1/2, be preferably 1/20～3/8 especially.

There is no particular limitation to the concentration of pigment particle lye, as long as can generate organic filler, but preferably with respect to the 1000m1 dispersion solvent, organic filler is 10～40000mg, and more preferably 20～30000mg is preferably 50～25000mg especially.

In addition, the preparative-scale during to the generation pigment particle is not particularly limited, and the combined amount of preferred poor solvent is the preparative-scale of 10～2000L, more preferably the preparative-scale of 50～1000L.

Particle diameter about organic filler, quantize and the method for expression group average-size thereby have by determination method, particle diameter as frequent use, performance distribute peaked particle diameter the most frequently, the meta particle diameter that is equivalent to the integral distribution curve central value, various mean grain size (number average, length is average, area is average, weight average, volume averaging etc.) etc. are arranged, in the present invention, if do not particularly point out, then mean grain size is meant number average bead diameter.The average particle of pigment particle (predecessor) is preferably 1nm～1 μ m, 1～200nm more preferably, and more preferably 2～100nm is preferably 5～80nm especially.Pigment particle can be a crystal particles, also can be non-crystal grain, can also be their potpourri.

In addition, as the index of expression particle monodispersity, short of in the present invention specifying, the ratio (Mv/Mn) of use volume average particle size (Mv) and number average bead diameter (Mn).The monodispersity of pigment particle (predecessor), promptly Mv/Mn is preferably 1.0～2.0, and more preferably 1.0～1.8, be preferably 1.0～1.5 especially.

As the particle size determination method of organic filler, can enumerate microscopic method, gravimetric method, light scattering method, light and block method, electric-resistivity method, sound equipment method, dynamic light scattering method, preferred especially microscopic method, dynamic light scattering method.As the microscope that uses in the microscopic method, for example can enumerate scanning electron microscope, transmission electron microscope etc.As the particle assay device that utilizes light scattering method, for example can enumerate day ダイ Na ミ Star Network light scattering photometer DLS-7000 series of the Na ノトラ Star Network UPA-EX150 ， Da mound electronics society manufacturing that machine dress society makes etc.

When the dispersion liquid of the above-mentioned pigment particle of preparation, preferably make and wherein contain spreading agent.To the operation that described dispersion liquid contains spreading agent is not particularly limited, preferably in organic pigment solution and poor solvent both or a side, adds spreading agent and it is contained.In addition, also preferably when forming pigment particle, utilize the system different to add dispersant solution with above-mentioned two kinds of liquid.Also preferred the use carried out the surface-treated pigment particles with spreading agent in advance, also can apply the surface treatment that can promote dispersant adsorption to pigment particles.Spreading agent has following effect: (1) is adsorbed on the surface of pigments of separating out quickly, forms fine nano particle, and (2) prevent that these particles from aggegation taking place again.

As operable spreading agent, for example can use the low molecule or the macromolecule dispersing agent of anionic, cationic, amphoteric ion type, nonionic or pigment derivative.In addition, also can use above-mentioned water-soluble polymers.Also have, the molecular weight of macromolecule dispersing agent is not particularly limited, as long as can allow this macromolecule dispersing agent to be dissolved in the solution equably, but preferred molecular weight is 1,000～2,000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, be preferably 10 especially, 000～100,000.As macromolecule dispersing agent, specifically can enumerate polyvinyl pyrrolidone, polyvinyl alcohol (PVA), polyvinyl methyl ether, polyethylene oxide, polyglycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate co-polymer, the part formolation thing of polyvinyl alcohol (PVA), the part butyral thing of polyvinyl alcohol (PVA), vinyl pyrrolidone-vinyl acetate co-polymer, the polyethylene oxide/propylene oxide segmented copolymer, polyacrylate, polyvinyl sulfate, poly-(4-vinylpridine) salt, polyamide, PAH salt, the condensation naphthalene sulfonate, cellulose derivative, starch derivative etc.In addition, can also use natural polymer subclasses such as alginate, gelatin, albumin, casein, Arabic gum, bassora gum (ト Application ガ Application ト go system), lignosulfonate.Wherein, preferably use above-mentioned water-soluble polymers, more preferably polyvinyl pyrrolidone.These macromolecules can be used singly or in combination of two or more.These spreading agents can use separately or use simultaneously.About the spreading agent that uses in the pigment dispersing, write up is in 29～46 pages of " evaluation of pigment dispersing stabilization と process for treating surface " (chemical corps intelligence association, distribution in Dec calendar year 2001).

As anionic dispersing agent (anionic surface active agent), can enumerate N-acyl-N-alkyltaurate, soap, alkyl sulfate salt, alkyl benzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinates, alkyl phosphate salt, naphthalene sulfonic acid-formaldehyde condensation product, polyxyethylated sulfuric acid etc.Wherein, preferred N-acyl-N-alkyltaurate.As the N-acyl-N-alkyltaurate, preferably be recorded in the Japanese kokai publication hei 3-273067 instructions those.These anionic dispersing agents can be used alone or in combination of two or more kinds.

Diamines that cationic dispersing agent (cation exchange surfactant) comprises quaternary ammonium salt, alkoxylate polyamines, fatty amine polyglycol ether, fatty amine, derived by fatty amine and aliphatic alcohol and polyamines, by the imidazoline of fatty acid derived and the salt of these cationic materials.These cationic dispersing agents can be used alone or in combination of two or more kinds.

The amphoteric ion type spreading agent is to have the cation radical spreading agent partly that contains in the anion base part that contains in the above-mentioned anionic dispersing agent molecule and the cationic dispersing agent molecule in the molecule simultaneously.

As non-ionic dispersing agent (non-ionics), can enumerate polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, fatty acid glyceride etc.Wherein, preferred polyoxyethylene alkylaryl ether.These non-ionic dispersing agents can be used alone or in combination of two or more kinds.

Pigment derivative type spreading agent be defined as by derive as the organic pigment of parent material, by this precursor structure being carried out the pigment derivative type spreading agent that chemical modification prepares, or the pigment derivative type spreading agent that forms through the pigmentation reaction by the pigment precursors of chemical modification.For example have and contain sugared pigment derivative type spreading agent, contain the pigment derivative type spreading agent that piperidyl pigment derivative type spreading agent Nai Huo perylene is derived, has the pigment derivative type spreading agent that is connected the structural functional group of pigment matrix by methylene, have the pigment matrix structure and the sulfonic pigment derivative type spreading agent that have carried out chemical modification with polymkeric substance, pigment derivative type spreading agent with sulfoamido, pigment derivative type spreading agent with ether, or has a pigment derivative type spreading agent of carboxylic acid group or carboxylic acid ester groups or carboxamide groups.

In good solvent, dissolve and when making organic pigment solution, the preferred existence simultaneously contains amino pigment dispersing agent.Here, amino comprises primary amine groups, secondary amino group, uncle's amino, and amino number can be 1, also can be for a plurality of.Containing amino pigment dispersing agent as this, can be to import the pigment derivative compound that forms behind the substituting group that contains amino on the pigment skeleton, also can be by containing amino monomer as aggregating into the polymer compound that branch forms.As their example, for example can enumerate the compound put down in writing in TOHKEMY 2000-239554 communique, 2003-96329 communique, 2001-31885 communique, Japanese kokai publication hei 10-339949 communique, the special open 5-72943 communique etc., but be not limited to these compounds.

Above-mentioned spreading agent can use at least a in the compound that is selected from following general formula (D1), (D3) and formula (D4) expression.

＜1, the compound of general formula (D1) expression 〉

General formula (D1)

A-N＝N-X-Y

In general formula (D1), A and X-Y represent to form the composition of azopigment simultaneously.Above-mentioned A can select arbitrarily, and the compound that forms azopigment so long as can carry out coupling with diazo-compounds gets final product.The object lesson of above-mentioned A as shown below, but the present invention never is confined to these structures.

Formula 1-1 formula 1-2

Formula 1-3 formula 1-4

Formula 1-5 formula 1-6 formula 1-7

Formula 1-8 formula 1-9 formula 1-10

Formula 1-11 formula 1-12

In general formula (D1), X represents singly-bound or is selected from following formula (i)～(divalent linker shown in the structural formula v).

(ii) formula is (iii) for formula (i) formula

(iv) formula is (v) for formula

In general formula (D1), Y represents the group shown in the following general formula (D2).

General formula (D2)

In general formula (D2), Z represents low-grade alkylidene.Z represents-(CH ₂) _b-, b represents 1～5 integer, is preferably 2 or 3.In general formula (D2) ,-NR ₂₁Expression low-grade alkyl amino or contain 5～6 yuan of saturated heterocyclyls of nitrogen-atoms.This-NR ₂₁During the expression low-grade alkyl amino, its expression-N (C _rH _2r+1) ₂, r represents 1～4 integer, preferably represents 1 or 2.-NR ₂₁When expression contains 5～6 yuan of saturated heterocyclyls of nitrogen-atoms, be preferably any heterocyclic radical that following structural formula is represented.

Pyridine ring piperidine ring morpholine ring

In above-mentioned general formula (D2), Z reaches-NR ₂₁Can have low alkyl group, alkoxy respectively as substituting group.In above-mentioned general formula (D2), a represents 1 or 2, preferably represents 2.

Below, list the object lesson of the compound of above-mentioned general formula (D1) expression, but the present invention never is confined to these object lessons.

The compound of general formula (D1) expression can synthesize by the method for putting down in writing in the TOHKEMY 2000-239554 communique for example.

＜2, the compound of general formula (D3) expression 〉

General formula (D3)

In general formula (D3),

Q represents to be selected from the organic pigment residue of anthraquinone compounds pigment, azo-compound pigment, phthalocyanine compound pigment, quinoline a word used for translation ketonic compound pigment, dioxazine compound pigment, anthracene pyrimidine (anthrapyrimidine) compound pigment, anthanthrone (anthanthrone) compound pigment, indanthrene compound pigment, yellow anthrone compound pigment, pyranthrone compound pigment, perylene ketonic compound pigment, perylene compound pigment and thioindigo compound pigment, wherein preferred azo-compound pigment Huo dioxazine compound pigment, more preferably azo-compound pigment.

X ₁Expression-CO-,-CONH-Y ₂-,-SO ₂NH-Y ₂-or-CH ₂NHCOCH ₂NH-Y ₂-, preferred-CO-,-CONH-Y ₂-.

Y ₂Expression can have substituent alkylidene or arlydene, wherein preferred phenylene, methylene phenyl or hexylidene, more preferably phenylene.

R ₁₁And R ₁₂Can be replacement or unsubstituted alkyl or R independently of one another ₁₁And R ₁₂Lump together and to form the heterocyclic radical that contains nitrogen-atoms at least.Wherein, preferable methyl, ethyl, propyl group or contain the pyridine radicals of nitrogen-atoms, more preferably ethyl.

Y ₁Expression-NH-or-O-.

Z ₁Group shown in expression hydroxyl or the general formula (D3a).Z when n1 is 1 ₁Can be-NH-X ₁-Q.M1 represents 1～6 integer, preferred 2～3.N1 represents 1～4 integer, preferred 1～2.

General formula (D3a)

In general formula (D3a), Y3 represents-NH-or-O-, m1, R ₁₁And R ₁₂Identical with its implication in general formula (D3).

As the compound of general formula (D3) expression, more specifically use-case such as following general formula are represented.

General formula (D3-1) (D3-6) in, Q, m1, n1, R ₁₁, R ₁₂Identical with its implication in general formula (D3).Below enumerate the object lesson of compound shown in the general formula (D3), but the present invention never is confined to this.Also have, the Cu-Pc in the formula represents copper phthalocyanine.

The compound of general formula (D3) expression for example can have R by making ₁₁And R ₁₂Amines and have a R ₁₁And R ₁₂Alcoholic compound and halogenation triaizine compounds react, the intermediate that obtains and dye compound reacted and form.In addition, can also be with reference to the record in the special fair 5-72943 instructions of Japan.

＜3, the pigment dispersing agent that contains graft copolymer 〉

Separating out when generating above-mentioned pigment particle, also preferred the use contained the graft copolymer that possesses amino and ether, the spreading agent that contains other composition of suitably selecting in case of necessity.

Above-mentioned graft copolymer has amino and ether at least, also can contain other monomer etc. as copolymer unit.

The matter average molecular weight of above-mentioned graft copolymer is preferably 3000～100000, and more preferably 5000～50000.If above-mentioned matter average molecular weight less than 3000 then can not prevent the aggegation of pigment particle, viscosity rises sometimes, if surpass 100000, and the dissolubility deficiency in organic solvent then, viscosity rises sometimes.

Preferred this graft copolymer contains (i) end at least to have the polyreactive oligomers of ethylenical unsaturated double bonds, (ii) has a monomer of amino and ethylenical unsaturated double bonds and (iii) have the polymerizable monomer of ether, as copolymer unit, also can contain (iv) other monomer in case of necessity as copolymerization units.

As the content of these copolymer unit in above-mentioned graft copolymer, preferably (i) above-mentioned polyreactive oligomers is 15～98 quality %, 25～90 quality % more preferably, the preferred monomer that (ii) contains amino is 1～40 quality %, more preferably 5～30 quality %, preferred (iii) above-mentioned polymerizable monomer with ether is 1～70 quality %, preferred 5～60 quality %.

If above-mentioned polyreactive oligomers contain quantity not sufficient 15 quality %, sometimes can not obtain steric repulsion effect as spreading agent, can not prevent the aggegation of pigment particle, if surpass 98 quality %, then the ratio of above-mentioned nitrogen containing monomer reduces, adsorptive power to organic filler reduces, and dispersed possibility is not enough.If above-mentioned nitrogen containing monomer contain quantity not sufficient 1 quality %, then the adsorptive power to organic filler is low, dispersed possibility is not enough, if surpass 40 quality %, then the ratio of above-mentioned polyreactive oligomers descends, therefore steric repulsion effect can not be obtained sometimes, the aggegation of organic filler can not be prevented as spreading agent.If above-mentioned polymerizable monomer with ether contain quantity not sufficient 1 quality %, then development adaptability may be not enough when the manufacturing of color filter etc., if surpass 70 quality %, then the ability as spreading agent may descend.

(i) polyreactive oligomers

Above-mentioned polyreactive oligomers (below, be sometimes referred to as " big monomer ".) be the oligomer that end has the group that contains ethylenical unsaturated double bonds.In the present invention, preferably in above-mentioned polyreactive oligomers, only there is a side to have the group that contains aforementioned ethylenical unsaturated double bonds in these oligomer two ends.

As above-mentioned oligomer, usually for example can enumerate the homopolymer that forms by at least a monomer that is selected from (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, styrene, vinyl cyanide, vinyl acetate and the butadiene or multipolymer etc., wherein homopolymer or multipolymer, the polystyrene etc. of preferred (methyl) alkyl acrylate.In the present invention, these oligomer can be substituted base and replace, and are not particularly limited for this substituting group, for example can enumerate halogen atom etc.

As above-mentioned group, can for example suitably enumerate (methyl) acryloyl group, vinyl etc., wherein preferred especially (methyl) acryloyl group with ethylenical unsaturated double bonds.

In the present invention, be preferably the oligomer of following general formula (E6) expression in the above-mentioned polyreactive oligomers.

In above-mentioned general formula (E6), R ⁶¹And R ⁶³Expression hydrogen atom or methyl.R ⁶²The expression carbon number is 1～8 and the alkylidene that can be replaced by alcoholic extract hydroxyl group, and preferred carbon number is 2～4 alkylidene.Y ⁶The expression phenyl, have phenyl that carbon number is 1～4 alkyl or-COOR ⁶⁴(R herein, ⁶⁴The expression carbon number be 1～6 and alkyl, phenyl or the carbon number that can be replaced by alcoholic extract hydroxyl group, halogen be 7～10 aralkyl.), preferred phenyl or-COOR ⁶⁴(R herein, ⁶⁴The expression carbon number is 1～4 and the alkyl that can be replaced by alcoholic extract hydroxyl group.)。Q represents 20～200.

As the object lesson of above-mentioned polyreactive oligomers, preferred poly-(methyl) acrylic acid 2-hydroxyl ethyl ester, polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, poly-(methyl) isobutyl acrylate, as they multipolymer be combined with the polymkeric substance of (methyl) acryloyl group a molecular end.

Above-mentioned polyreactive oligomers can be commercially available; or suitably synthetic; as the commercially available prod; for example can enumerate single terminal methyl group acryloyl group polystyrene oligomer (Mn=6000; trade name: AS-6; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryloyl group polymethyl methacrylate oligomer (Mn=6000; trade name: AA-6; East Asia synthetic chemical industry (strain) society system); the positive butyl ester oligomer of single terminal methyl group acryloyl group polypropylene (Mn=6000; trade name: AB-6; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryloyl group polymethylmethacrylate/methacrylic acid 2-hydroxyl ethyl ester oligomer (Mn=7000; trade name: AA-714; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryloyl group poly-n-butyl methacrylate/methacrylic acid 2-hydroxyl ethyl ester oligomer (Mn=7000; trade name: 707S; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryloyl group polymethylacrylic acid 2-Octyl Nitrite/methacrylic acid 2-hydroxyl ethyl ester oligomer (Mn=7000; trade name: AY-707S; AY-714S, East Asia synthetic chemical industry (strain) society system) etc.

In the present invention; preferred object lesson as above-mentioned polyreactive oligomers; can enumerate as at least a kind of oligomer in the multipolymer of the polymkeric substance, (methyl) alkyl acrylate and the polystyrene that are selected from (methyl) alkyl acrylate; and number-average molecular weight is 1000～20000, and end has the oligomer of (methyl) acryloyl group.

(ii) contain amino monomer

Contain amino monomer as above-mentioned, can be fit to enumerate at least a in the compound that for example is selected from following general formula (E2) expression.

In above-mentioned general formula (E2), R ²¹Expression hydrogen atom or methyl.R ²²The expression carbon number is 1～8 alkylidene, and wherein preferred carbon number is 1～6 alkylidene, and preferred especially carbon number is 2～3 alkylidene.

X ²Expression-N (R ²³) (R ²⁴) ,-R ²⁵N (R ²⁶) (R ²⁷).Herein, R ²³And R ²⁴Expression hydrogen atom, carbon number are 1～6 alkyl or phenyl.R ²⁵The expression carbon number is 1～6 alkylidene, R ²⁶And R ²⁷Expression hydrogen atom, carbon number are 1～6 alkyl or phenyl.

In foregoing ,-N (R ²³) (R ²⁴) in R ²³And R ²⁴Be preferably hydrogen atom or carbon number and be 1～4 alkyl or phenyl ,-R ²⁵-N (R ²⁶) (R ²⁷) in R ²⁵Be preferably carbon number and be 2～6 alkylidene, R ²⁶And R ²⁷Be preferably carbon number and be 1～4 alkyl or phenyl.M2 and n2 represent 1 or 0, preferred m2=1 and n2=1, or m2=1 and n2=0 (that is the monomer of representing corresponding to following general formula (E3), (E4)).

In the present invention, the monomer of above-mentioned general formula (E2) expression is preferably and is selected from following (E3) and (E4) at least a in the monomer represented of arbitrary formula.

In above-mentioned general formula (E3), R ³¹And R ²¹Synonym.R ³²And R ²²Synonym.X ³With X ²Synonym.

In above-mentioned general formula (E4), R ⁴¹And R ²¹Synonym.X ⁴With X ²Synonym is preferably-N (R ⁴³) (R ⁴⁴) (R herein, ⁴³And R ⁴⁴With R ²³And R ²⁴Synonym.) or-R ⁴⁵-N (R ⁴⁶) (R ⁴⁷) (R herein, ⁴⁵, R ⁴⁶And R ⁴⁷Respectively with R ²⁵, R ²⁶And R ²⁷Synonym.)。

Object lesson as the monomer of above-mentioned general formula (E2) expression, can enumerate dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, diisopropyl (methyl) acrylamide, di-n-butyl (methyl) acrylamide, diisobutyl (methyl) acrylamide, morpholino base (methyl) acrylamide, piperidino (methyl) acrylamide, N-methyl-2-pyrrolidinyl (methyl) acrylamide and N, N-aminomethyl phenyl (methyl) acrylamide (above is (methyl) acrylic amide); 2-(N, the N-dimethylamino) ethyl (methyl) acrylamide, 2-(N, the N-diethylamino) ethyl (methyl) acrylamide, 3-(N, the N-diethylamino) propyl group (methyl) acrylamide, 3-(N, the N-dimethylamino) propyl group (methyl) acrylamide, 1-(N, the N-dimethylamino)-1,1-dimethyl methyl (methyl) acrylamide, 6-(N, N-dimethylamino) hexyl (methyl) acrylamide (above is aminoalkyl (methyl) acrylic amide) etc. are as preferred monomers.

The polymerizable monomer that (iii) has ether

As above-mentioned polymerizable monomer, can suitably enumerate at least a of the monomer that for example is selected from following general formula (E1) expression with ether.

In above-mentioned general formula (E1), R ¹¹Expression hydrogen atom or methyl.R ¹²The expression carbon number is 1～8 alkylidene, and wherein preferred carbon number is 1～6 alkylidene, and more preferably carbon number is 2～3 alkylidene.X ¹Expression-OR ¹³Or-OCOR ¹⁴Herein, R ¹³Expression hydrogen atom, carbon number are 1～18 alkyl, phenyl or are the phenyl that 1～18 alkyl replaces by carbon number.R ¹⁴The expression carbon number is 1～18 alkyl.In addition, m3 represents 2～200, preferred 5～100, preferred especially 10～100.

To as above-mentioned polymerizable monomer with ether, there is no particular limitation, so long as the monomer that has ether and have a polymerism gets final product, can from common monomer, select, for example can enumerate polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyglycol polypropylene glycol list (methyl) acrylate, polytetramethylene glycol monomethacrylates etc., these monomers can be commercially available or suitably synthetic.As the commercially available prod, can enumerate methoxy polyethylene glycol methacrylate-styrene polymer (trade name: NK エステ Le M-40G, M-90G, M-230G (more than, East Asia synthetic chemical industry (strain) society system); Trade name: Block レ Application マ one PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (more than, Japan grease (strain) society system)), polyethylene glycol monomethacrylate (trade name: Block レ Application マ one PE-90, PE-200, PE-350, Japan grease (strain) society system), polypropylene glycol monomethacrylate (trade name: Block レ Application マ one PP-500, PP-800, PP-1000, Japan grease (strain) society system), polyglycol polypropylene glycol monomethacrylate (trade name: Block レ Application マ one 70PEP-370B, Japan grease (strain) society system), polyglycol polytetramethylene glycol monomethacrylates (trade name: Block レ Application マ one 55PET-800, Japan grease (strain) society system), polypropylene glycol polytetramethylene glycol monomethacrylates (trade name: Block レ Application マ one NHK-5050, Japanese grease (strain) society system) etc.

(iv) other monomer

Above-mentioned graft copolymer can also contain above-mentioned other monomer as copolymer unit, there is no particular limitation to this other monomer, can select according to purpose, for example (for example can enumerate aromatic ethenyl compound, styrene, α-Jia Jibenyixi and vinyltoluene), (methyl) alkyl acrylate (for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate and (methyl) isobutyl acrylate), (methyl) acrylic acid alkyl aryl ester (for example, (methyl) acrylic acid benzyl ester), (methyl) glycidyl acrylate, vinyl esters of carboxylic acids (for example, vinyl acetate and propylene and ethylene base ester), vinyl nitrile (for example, (methyl) vinyl cyanide and α-Lv Daibingxijing), the aliphatics conjugated diolefine (for example, 1,3-butadiene and isoprene), (methyl) acrylic acid etc.Wherein preferred unsaturated carboxylic acid, (methyl) alkyl acrylate, (methyl) acrylic acid alkyl aryl ester and vinyl esters of carboxylic acids.

As the content of this other monomer in the above-mentioned graft copolymer, for example be preferably 5～70 weight %.If this containing ratio less than 5 weight % then can not control the rerum natura of coated film sometimes, if above 70 weight %, then can not give full play to the ability as spreading agent sometimes.

As the preferred object lesson of above-mentioned graft copolymer, can enumerate

(11) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate,

(12) 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate polystyrene copolymer,

(13) 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/(methyl) methyl acrylate/terminal methyl group propylene acidylate polystyrene copolymer,

(14) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate (methyl) methyl acrylate and methacrylic acid 2-hydroxyl ethyl ester multipolymer,

(15) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate methyl methacrylate and methacrylic acid 2-hydroxyl ethyl ester multipolymer,

(16) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate methyl methacrylate and methacrylic acid 2-hydroxyl ethyl ester multipolymer,

(17) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polypropylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(18) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyglycol polypropylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(19) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyglycol polytetramethylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(20) 3-(N, N-dimethylamino) propyl group acrylamide/polypropylene glycol polytetramethylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate is gathered (methyl) methyl acrylate copolymer etc.

Wherein, preferred (11), (14), (18), the compound of more preferably following formula (D4) expression.In the formula (D4), Me represents methyl.

Formula (D4)

A: b: c=15: 20: 65 (weight ratio)

Above-mentioned graft copolymer can obtain by making the composition that will form above-mentioned each copolymer unit for example carry out free radical polymerization in solvent.This radical polymerization is fashionable carrying out, and can use radical polymerization initiator, in addition, can also use chain-transferring agent (for example, 2 mercapto ethanol and lauryl mercaptan).For the pigment dispersing agent that contains graft copolymer, can be with reference to the record of TOHKEMY 2001-31885 communique.

In order further to improve the uniformly dispersed and bin stability of pigment particle, as spreading agent content, preferably the pigment with respect to 100 mass parts is 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.If less than 0.1 mass parts then may be can't see the raising of pigment particle dispersion stabilization.In addition, spreading agent can use separately, also can make up several and use.

In order further to improve the uniformly dispersed and bin stability of organic filler, as spreading agent content, preferably the organic filler with respect to 100 mass parts is 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.If less than 0.1 mass parts then may be can't see the raising of pigment particle dispersion stabilization.

[concentrating]

By above-mentioned pigment particle dispersion liquid is carried out desalination and concentration, can be suitable for the concentrate of color filter coating fluid and ink for inkjet with industrial-scale production.

Method for concentration is had no particular limits, as long as can concentrate pigment particle liquid, for example preferably in the pigment particle dispersion liquid, add and extract solvent and mixing, with the pigment particle concentration extraction to this extract solvent mutually in, and form the method for concentrated nano particle liquid with this concentrated extracting solution of filtration such as filtrator; The method of utilizing centrifuging to make the pigment particle sedimentation and concentrating; Utilize ultrafiltration to carry out the method for desalination and concentration; The method that solvent distillation is concentrated by vacuum freeze drying; Make method that solvent seasoning concentrates etc. by heating or decompression.Or very preferably use the combination of these methods.

Concentration about the pigment particle after concentrating is preferably 1～100 quality %, and more preferably 5～100 quality % are preferably 10～100 quality % especially.

There is no particular limitation to the extraction solvent that uses in this concentration extraction, but in fact with the dispersion solvent of pigment particle dispersion liquid (for example, aqueous solvent) do not mix (in the present invention, do not take place in fact to mix and be meant that compatibility is low, meltage is preferably below the 50 quality %, more preferably below the 30 quality %.This meltage does not have special lower limit, if but the dissolubility of consideration usual solvents, then the lower limit of this meltage is actually more than the 1 quality %.After mixing, form the interface when leaving standstill) solvent be preferred.In addition, preferred this extraction solvent is pigment particle is scattered in again extract the solvent that also produces weak aggegation (even not applying the flocculate that high shear force also can disperse again by grind or high-speed stirred etc.) in the solvent.If reach this state, then can not form the strong aggegation that particle size is changed, available extraction wet with solvent purpose pigment particle can easily remove the diffusing solvent of the five equilibrium that anhydrates by filtering to wait on the other hand, and from these aspects, described solvent is preferred.As extracting solvent, preferred ester compounds solvent, alcoholic compound solvent, aromatic compound solvent, fatty compound solvent, more preferably ester compounds solvent, aromatic compound solvent or fatty compound solvent, especially preferably ester compounds solvent.

As the ester compounds solvent, for example can enumerate 2-(1-methoxyl) propyl group acetate, ethyl acetate, ethyl lactate etc.The operation alcoholic compound for example can be enumerated normal butyl alcohol, isobutyl alcohol etc.As aromatics, for example can enumerate benzene,toluene,xylene etc.As fatty compound, for example can enumerate normal hexane, cyclohexane etc.In addition, the extraction solvent can be the single solvent in the above-mentioned preferred solvent, also can be the mixed solvent that is formed by multiple solvent.

The amount of extracting solvent is not particularly limited, as long as can extract above-mentioned pigment particle, considers concentration extraction, preferably its amount ratio pigment particle dispersion liquid still less.If represent with volume ratio, then the pigment particle dispersion liquid was made as 100 o'clock, the extraction solvent that is added is preferably 1～100, and more preferably 10～90, be preferably 20～80 especially.If too much, then concentrating needs a large amount of time, if very few, then extract insufficient, residual nano particle in the dispersion solvent.

After adding the extraction solvent,, preferably mix in order fully to contact with dispersion liquid.Mix and to use usual way.There is no particular limitation to adding the temperature of extracting solvent and mixing when, but be preferably 1～100 ℃, more preferably 5～60 ℃.For interpolation, the mixing of extracting solvent, just can use any device as long as can implement each operation satisfactorily, for example can use separating funnel type device to carry out.

Under the situation that adopts ultrafiltration, for example can use the desalination/concentrated method that is used for silver halide.Open (Research Disclosure) No.10208 (1972), No.13122 (1975) and No.16351 (1977) are studied in known having.For pressure differential and flow as the important operation condition, can publish (1978) with reference to the big spring man of virtue and ability of arrow work " film utilizes technology Ha Application De Block Star Network " good fortune study, the family curve of putting down in writing among the p275 is selected, but disperse the object space face at the processing target pigment particle, in order to suppress the aggegation of particle, also need to find out optimum condition.In addition, with regard to replenishing, the constant volume formula of continuous interpolation solvent and the batch-type that gradation is intermittently added are arranged, but the preferred desalting processing time is than the constant volume formula of weak point because of film sees through for the method for the solvent that lose.Solvent for replenishing thus can use the pure water that obtains by ion-exchange or distillation, but also can sneak into the poor solvent of spreading agent, spreading agent in pure water, also can directly add organic nano particle to and disperse in the thing.

As ultra filtration membrane, ultra filtration membrane such as plate, the screw type of packing into, cylinder type, macaroni yarn type, hollow fiber type as module, there are society of Asahi Chemical Industry's (strain), ダイセ Le chemistry (strain) society, (strain) DongレShe, (strain) day Dong Diangongshe etc. to sell, but on total membrane area and cleaning, preferred screw type or macaroni yarn type ultra filtration membrane.In addition,, must determine, be preferably more than 5,000 below 50,000, more preferably more than 5,000 below 15,000 according to the molecular weight of employed spreading agent as the molecular cut off of the threshold value index of membrane-permeable composition.

For the dispersion solvent with the pigment particle dispersion liquid separates with concentrated extracting solution, preferably carry out filtrator and filter.As the filtration unit that filtrator uses, for example can use the device of pressure filtration and so on.As preferred filtrator, can enumerate nanofilter, ultrafilter etc.Preferably filter, remove residual dispersion solvent, the pigment particle in the concentrated extracting solution is concentrated and forms concentrated nano particle liquid by filtrator.

There is no particular limitation to freeze-drying method, any method that can use those skilled in the art to adopt.For example, can enumerate refrigerant direct expansion method, repeated freezing method, heating agent round-robin method, triple heat-exchanging method, indirect heating freezing, but preferably use refrigerant direct expansion method, indirect heating freezing, more preferably use the indirect heating freezing.All preferably after carrying out precooling, carry out freeze drying in any method.There is no particular limitation to the precooling condition, and to carry out cryodesiccated sample freezing equably but must make.

Device as the indirect heating freezing, can enumerate small frozen dryer, FTS freeze drier, LYOVAC freeze drier, experiment freeze drier, research freeze drier, triple heat interchange vacuum freeze drier, single-cooling type freeze drier, HULL freeze drier, but preferably small frozen dryer, experiment with freeze drier, research with freeze drier, single-cooling type freeze drier, preferred small frozen dryer, single-cooling type freeze drier.

There is no particular limitation to cryodesiccated temperature, for example is-190～about-4 ℃ approximately, and preferred-120～about-20 ℃ approximately, more preferably from about-80～approximately-60 ℃.Also there is no particular limitation to cryodesiccated pressure, and those skilled in the art can suitably select, for example can be at about 0.1～about 35Pa, and preferred about 1～about 15Pa more preferably from about carries out under 5～about 10Pa.Sublimation drying is for example about 2～about 48 hours, preferred about 6～about 36 hours, and more preferably from about 16～about 26 hours.Certainly, these conditions can suitably be selected by those skilled in the art.About freeze-drying, can reference example such as pharmaceutical machine technology Ha Application De Block Star Network: pharmaceutical machine technical research meeting be compiled, book shop, people from ground, p.120～129 (in September, 2000); Vacuum Ha Application De Block Star Network: ULVAC Corp compiles, オ-system society, p.328～331 (1992); Freezing and drying study Hui Hui Chi: she controls him at the rattan filial piety, No.15, p.82 (nineteen sixty-five) etc.

As concentrating the centrifugal separator that uses in the pigment particle,, can use any device as long as can make the pigment particle sedimentation in the pigment particle dispersion liquid (or pigment particle concentrated extracting solution) by centrifuging.As centrifugal separator, for example, outside fexible unit, the centrifugal separator etc. that can enumerate the hydro-extractor of the skin function of taking (suction supernatant layer in rotation, and be discharged into system outer function with it) and discharge solid content continuously.

As the condition of centrifuging, centrifugal force (be expressed as need times over the value of the centrifugal acceleration of acceleration of gravity) is preferably 50～10000, and more preferably 100～8000, be preferably 150～6000 especially.Temperature during centrifuging depends on the solvent species of dispersion liquid, but is preferably-10～80 ℃, more preferably-5～70 ℃, is preferably 0～60 ℃ especially.

There is no particular limitation for the device that uses when concentrating pigment particle by drying under reduced pressure, as long as can make the solvent evaporation of pigment particle dispersion liquid (or pigment particle concentrated extracting solution).Thereby for example can enumerate general vacuum dryer and rotary pump and on one side agitated liquid heat on one side drying under reduced pressure device, can make the pipe of liquid by the heating decompression carry out the device etc. of continuous drying.

Heating drying under reduced pressure temperature is preferably 30～230 ℃, more preferably 35～200 ℃, is preferably 40～180 ℃ especially.Pressure during decompression is preferably 100～100000Pa, and more preferably 300～90000Pa is preferably 500～80000Pa especially.

According to above-mentioned method for concentration, can concentrate out pigment particle from the pigment particle dispersion liquid effectively.About concentration rate,, then can be concentrated into the concentration that concentrates in the pigment particle paste and be preferably about 100～about 3000 times, more preferably about 500～about 2000 times if for example will be made as 1 as the nano particle concentration in the pigment particle dispersion liquid of raw material.

[fine dispersion]

Concentrate etc. by above-mentioned, when pigment particle is in state of aggregation, preferably carry out fine decentralized (in the present invention, fine dispersion is to instigate the particles aggregate in the dispersion liquid to be scattered, and improves dispersion degree).

Concentrate organic filler contained in the organic filler liquid that forms by said extracted solvent, centrifuging, drying etc. and can aggegation take place because of concentrating usually.At this moment, become possibility for rapid filter is filtered, obtain good disperse state once more, preferred above-mentioned pigment particle obtains with floccus.Herein, floccus is meant with the degree that can disperse again and condenses the particulate aggregate that (soft cohesion) becomes very weakly.By making this pigment particle become floccus, just can with from as water base mixed liquor the organic pigment particulate of separating out filter soon etc., thereby from medium, separate.And then the floccus of separating (soft condensed matter) is scattered in again in the organic solvent of suitable manufacturing color filter, thereby form organic solvent based pigment dispensing composition (non-water-based dispersed composition) expeditiously.That is, when the mixed solvent of good solvent and poor solvent is water-based solvent, can expeditiously it be replaced into the 3rd solvent that constitutes by organic solvent, realize the switching of dispersion medium (external phase).The mean grain size of floccus does not limit especially, but considers above-mentioned filterableness, is preferably 0.5～500 μ m, 5～100 μ m more preferably.In addition, in the present invention, be generically and collectively referred to as " the 3rd solvent " with either party different solvent in above-mentioned good solvent (the 1st solvent) and the described poor solvent (the 2nd solvent).

In addition, adopt the micronize of the resulting degree of scatter of decentralized method commonly used insufficient, be necessary the method that adopts miniaturization efficient higher.The organic filler that is in strong state of aggregation is (among the present invention, the cohesion organic filler is meant the material that organic filler such as condensed matter gathers together and forms under the effect of secondary force, when being the nanometer size, predecessor is also referred to as the cohesion nano particle), by contain the quality mean molecular weight in cohesion organic filler liquid is macromolecular compound more than 1000, can make organic filler fine suitably decentralized, form and disperse thing (among the present invention, cohesion organic filler liquid is meant and contains the material that condenses organic filler in liquid, it can be dispersion liquid, concentrate, stick with paste, slurries etc. are as long as contain the cohesion organic filler).The words that are described in further detail, by utilizing above-mentioned macromolecular compound, when pigment particles is separated out in the mixed liquor of good solvent and poor solvent, have good fine dispersiveness (can realize evenly and the characteristic of nominal particle size) and dispersion stabilization (can keep for a long time evenly and the characteristic of nominal particle size), after medium is changed into the organic solvent that is suitable for color filter, it being disperseed again, above-mentioned characteristic still can keep, thereby makes color filter realize high-performance.And the optical characteristics that above-mentioned macromolecular compound can the overslaugh color filter etc. do not interact with the coloring of organic pigment particulate, so can make color filter and liquid crystal indicator realize high-performance yet.

Described macromolecular compound is preferably the macromolecular compound of following general formula (1) expression.

(A ¹-R ² _nR ¹ P ¹) _mGeneral formula (1)

In above-mentioned general formula (1), A ¹Expression has 1 valency organic group of the group of selecting from acidic-group, the group that has basic nitrogen atom, urea groups, urethano, the group of band coordination oxygen atom, carbon number are alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl 4 or more, or represents to contain the 1 valency organic group that substituent organic pigment structure or heterocycle can be arranged.N A ¹Can be identical, also can be different.

Specifically, though to A ¹Have no particular limits, but as above-mentioned " 1 valency organic group " with acidic-group, can enumerate for example have the carboxylic acid group, the 1 valency organic group of sulfonic group, sulfate mono ester group, phosphate, phosplate base, boronate etc.In addition, as above-mentioned " 1 valency organic group ", can enumerate and for example have amino (NH with the group that has basic nitrogen atom ₂) 1 valency organic group, have substituted imine base (NHR ⁸,-NR ⁹R ¹⁰) 1 valency organic group (wherein, R ⁸, R ⁹And R ¹⁰Independent separately expression carbon number is that the alkyl below 20 more than 1, carbon number are that the aryl below 20 or carbon number are the aralkyl below 30 more than 7 more than 6.), have the guanidine radicals of following general formula (a1) expression 1 valency organic group [in the general formula (a1), R ^A1, R ^A2Independent separately expression carbon number is that the alkyl below 20 1 or more, carbon number are that the aryl below 20 or carbon number are the aralkyl below 30 more than 7 more than 6], have the amidino groups that following general formula (a2) represents 1 valency organic group [in the general formula (a2), R ^A3, R ^A4Independent separately expression carbon number is that the alkyl below 20 more than 1, carbon number are that the aryl below 20 or carbon number are the aralkyl below 30 more than 7 more than 6] etc.

As above-mentioned " 1 valency organic group ", for example can enumerate-NHCONHR with urea groups ¹⁵(wherein, R ¹⁵Expression hydrogen atom, carbon number are that the alkyl below 20 or carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7 more than 1.) etc.

As above-mentioned " 1 valency organic group ", for example can enumerate-NHCOOR with urethano ¹⁶,-OCONHR ¹⁷(wherein, R ¹⁶And R ¹⁷Be that the alkyl below 20 more than 1, carbon number are that the aryl below 20 or carbon number are the aralkyl below 30 more than 7 more than 6 for carbon number independently of one another.) etc.

As above-mentioned " 1 valency organic group ", for example can enumerate the group with acetylacetonate group, group etc. with crown ether with " group of band coordination oxygen atom ".

As above-mentioned " having carbon number is 1 valency organic group of the alkyl more than 4 ", can enumerate carbon number and be more than 4 alkyl (for example, octyl group, dodecyl etc.), carbon number is that aryl (for example, phenyl, naphthyl etc.), carbon number more than 6 is aralkyl (for example, benzyl etc.) more than 7 etc.The carbon number of this moment does not have the upper limit, but is preferably below 30.

As above-mentioned " 1 valency organic group ", for example can enumerate group with trimethoxysilyl, triethoxysilyl etc. with alkoxysilyl.

As above-mentioned " 1 valency organic group ", for example can enumerate group with glycidyl etc. with epoxy radicals.

As above-mentioned " 1 valency organic group ", for example can enumerate 3-isocyanato-propyl group etc. with isocyanate group.

As above-mentioned " 1 valency organic group ", for example can enumerate 3-hydroxypropyl etc. with hydroxyl.

As above-mentioned A ¹, preferred acidic group, the basic group that has nitrogen-atoms, urea groups or carbon number are 1 valency organic group of the alkyl more than 4.

In addition, above-mentioned organic pigment structure or heterocycle are not particularly limited, more particularly, as the organic pigment structure, can enumerate for example phthalocyanine compound, insoluble azo-compound, azo lake compound, anthraquinone compounds, quinoline a word used for translation ketonic compound, dioxazine compound, diketopyrrolo-pyrrole compound, anthracene pyridine compounds, anthanthrone (anthanthrone) compound, indanthrene compound, yellow anthrone compound, perylene ketonic compound, perylene compound, thioindigo compound etc.In addition, as heterocycle, for example can enumerate thiophene, furans, xanthene, pyrroles, pyrrolin, pyrrolidine, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles, oxazole, thiazole, oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines, diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoins, indoles, quinoline, carbazole, acridine, acridone, anthraquinone etc.

In addition, above-mentioned organic pigment structure or heterocycle can have substituting group T, as this substituting group T, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl, carbon number such as phenyl, naphthyl is 6～16 aryl, carbon numbers such as acetoxyl group are 1～6 acyloxy, carbon number such as methoxyl, ethoxy is 1～6 alkoxy, and halogen atoms such as chlorine, bromine, carbon numbers such as methoxycarbonyl group, carbethoxyl group, hexamethylene oxygen carbonyl are 2～7 alkoxy carbonyl group, cyano group, carbonate group, hydroxyls such as the carbonic acid tert-butyl ester, amino, carboxyl, sulfoamido, N-sulfoamido etc.

In addition, as above-mentioned A ¹, be preferably the group that following general formula (4) is represented.

(B ¹ _A1R ¹⁸-general formula (4)

In above-mentioned general formula (4), B ¹The group that expression is selected from acidic-group, the group that has basic nitrogen atom, urea groups, urethano, the group with coordination oxygen atom, carbon number are alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl more than 4, or expression can have substituent organic pigment structure or heterocycle, R ¹⁸The organic or inorganic linking group of expression singly-bound or a1 valency.A1 represents 1～5, a1 B ¹Can be identical, also can be different.

The preferred scheme of represented group and above-mentioned A in the general formula (4) ¹Synonym.

R ¹⁸The linking group of expression singly-bound or a1+1 valency.A1 represents 1～5.As connecting basic R ¹⁸, comprise by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom, and 0～20 group that sulphur atom constitutes can not have replacement, can have substituting group yet.R ¹⁸Be preferably organic linking group.

As R ¹⁸Object lesson, the group that can enumerate following structural unit or combine by following structural unit.And, this linking group R ¹⁸Also can have above-mentioned substituting group T.

-O- -S-

(t-1) (t-2) (t-3)(t-4)(t-5)(t-6) (t-7)(t-8) (t-9) (t-10) (t-11) (t-12)

(t-13) (t-14) (t-15) (t-16) (t-17) (t-18) (t-19)

-G＝N-

(t-20) (t-21) (t-22) (t-23) (t-24) (t-25) (t-26)

(t-27)(t-28)(t-29)(t-30) (t-31) (t-32) (t-33) (t-34)

In above-mentioned general formula (1), R ¹The connection base of expression (m+n) valency.M+n equals 3～10.

As above-mentioned R ¹The connection base of (m+n) valency of expression comprises by 1～100 carbon atom, 0～10 nitrogen-atoms, and 0～50 oxygen atom, 1～200 hydrogen atom, and 0～20 group that sulphur atom constitutes can not have replacement, can have substituting group yet.R ¹Be preferably organic linking group.

As R ¹Object lesson, the group (can also form ring texture) that can enumerate the group of above-mentioned (t-1)～(t-34) or form by several these moiety combinations.Above-mentioned linking group R ¹When having substituting group,, can enumerate above-mentioned substituting group T as this substituting group.

R ²Expression singly-bound or divalent linking group.As R ², comprise by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom, and 0～20 group that sulphur atom constitutes can not have replacement, can have substituting group yet.As R ²Object lesson, the group that can enumerate the group shown in above-mentioned t-3～5,7～18,22～26,32,34 or form by several these moiety combinations, and preferably with R ¹Link position on have sulphur atom.Above-mentioned R ²When having substituting group,, can enumerate above-mentioned substituting group T as this substituting group.

In above-mentioned general formula (1), m represents 1～8.M is preferably 1～5, and more preferably 1～3, be preferably 1～2 especially.

In addition, n represents 2～9.N is preferably 2～8, and more preferably 2～7, be preferably 3～6 especially.

In above-mentioned general formula (1), P ¹The expression macromolecular scaffold can suitably be selected from common polymkeric substance etc.

In polymkeric substance, in order to constitute macromolecular scaffold, be preferably selected from polymer of vinyl monomer or multipolymer, the ester compounds base polymer, the ether compound base polymer, the urethanes base polymer, the amide compound base polymer, the epoxy compound base polymer, the organo-silicon compound base polymer, and their modifier or multipolymer [for example comprise, polyethers/polyurethane copolymer, the multipolymer of polyethers/polymers of vinyl monomers etc. (can be a random copolymers, segmented copolymer, in the graft copolymer any)] at least a in, more preferably be selected from polymer of vinyl monomer or multipolymer, the ester compounds base polymer, the ether compound base polymer, at least a in urethanes base polymer and their modifier or the multipolymer, special preferred vinyl polymer of monomers or multipolymer.

And preferred above-mentioned polymkeric substance dissolves in the organic solvent.And if the compatibility of organic solvent is low, when then for example using, a little less than the compatibility of dispersion medium, can not guarantee the sufficient adsorbed layer of stably dispersing sometimes as pigment dispersing agent.

In addition, preferably with R ¹Link position on have sulphur atom.

In the macromolecular compound of above-mentioned general formula (1) expression, more preferably by the macromolecular compound of following general formula (2) expression.

(A ²-R ⁴-S  _xR ³ S-R ⁵-P ²) _yGeneral formula (2)

In above-mentioned general formula (2), A ²With the A in the above-mentioned general formula (1) ¹Synonym, its concrete preferred version is also identical.In addition, A ²Also can have substituting group, can enumerate above-mentioned substituting group T.

In above-mentioned general formula (2), R ³The linking group of expression (x+y) valency.R ³With R ¹Synonym, preferred version are also identical.At this moment, R ³The linking group of expression x+y valency, the value of x and preferred version are identical with n in the general formula (1), the m synonym in the value of y and preferred version and the general formula (1), the m+n synonym in the value of x+y and preferred version and the general formula (1).

R ³The linking group of expression is preferably organic connection base, and the preferred object lesson of this organic linking group is as follows.But, in that the present invention is not limited thereto.

Aspect acquired, the synthetic easiness of raw material, dissolubility all kinds of solvents, the group of preferably above-mentioned (r-1), (r-2), (r-10), (r-11), (r-16), (r-17) in above-mentioned group.

In addition, above-mentioned R ³When having substituting group,, can enumerate above-mentioned substituting group T as this substituting group.

In above-mentioned general formula (2), R ⁴And R ⁵The linking group of representing singly-bound or divalent independently of one another.

As above-mentioned R ⁴, R ⁵The expression " linking group of divalent ", can enumerate have substituent, the alkylidene of straight chain, side chain or ring-type, arlydene or inferior aralkyl ,-O-,-S-,-C (=O)-,-N (R ¹⁹)-,-SO-,-SO ₂-,-CO ₂-or-N (R ²⁰) SO ₂-, or the divalent group that these two or more moiety combinations form is as preferred example (above-mentioned R ¹⁹And R ²⁰Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl.)。Wherein preferred organic linking group.

As above-mentioned R ⁴, more preferably the alkylidene of straight or branched or inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹)-,-SO ₂-,-CO ₂-or-N (R ²⁰) SO ₂-, or the divalent group that forms of these two or more moiety combinations, be preferably especially the alkylidene of straight or branched or inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹)-,-CO ₂-, or the divalent group that forms of these two or more moiety combinations.

As above-mentioned R ⁵, more preferably the alkylidene of singly-bound, straight or branched, inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹)-,-SO ₂-,-CO ₂-or-N (R ²⁰) SO ₂-, or the divalent group that forms of these two or more moiety combinations, be preferably especially the alkylidene of straight or branched, inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹)-or-CO ₂-, or the divalent group that forms of these two or more moiety combinations.

In addition, above-mentioned R ², R ⁵When having substituting group,, can enumerate above-mentioned substituting group T as this substituting group.

In addition, the P in the above-mentioned general formula (2) ²The expression macromolecular scaffold can suitably be selected from common polymkeric substance etc.About the preferred version of polymkeric substance, with the P in the above-mentioned general formula (1) ¹Synonym, preferred version are also identical.

In the macromolecular compound of above-mentioned general formula (2) expression, preferred especially R ³For above-mentioned object lesson (r-1), (r-2), (r-10), (r-11), (r-16) or (r-17), R ⁴For the alkylidene of singly-bound, straight or branched or inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹)-or-CO ₂-or the divalent group that forms of these two or more moiety combinations, R ⁵For singly-bound, ethylidene, propylidene or following general formula (s-a) or (s-b) expression linking group, P ²Be polymer of vinyl monomer or multipolymer, ester compounds base polymer, ether compound base polymer, polyurethane polymer or their modifier, y is 1～2, and x is 3～6 macromolecular compound.Also have, in the following radicals, R ²¹Expression hydrogen atom or methyl, 1 expression 1 or 2.

The quality mean molecular weight of above-mentioned macromolecular compound is more than 1000, but the preferred mass mean molecular weight is 3000～100000, more preferably 5000～80000, be preferably 7000～60000 especially.If the quality mean molecular weight is in the above-mentioned scope, then can give full play to the effect of a plurality of functional groups of polymer ends importing, the adsorbability of solid surface, micella being formed the excellent performance of performance aspect ability, the surfactivity, can obtain good dispersiveness and dispersion stabilization.

The object lesson of the compound of general formula (1) expression is as follows.But the present invention never is confined to these object lessons.

In addition, be macromolecular compound more than 1000 as above-mentioned molecular weight, can use following macromolecular compound (following sometimes this compound the abbreviation made " macromolecular compound that contains acidic-group ") with acidic-group.As this macromolecular compound, be preferably macromolecular compound, more preferably contain (A) by at least a the reaching in the repetitive of compound deriving (B) by at least a copolymerization in the repetitive of compound deriving with carboxylic acid ester groups with carboxyl with carboxyl.

As (A) repetitive by compound deriving with carboxyl, be preferably the repetitive of following general formula (I) expression, more preferably by acrylic or methacrylic acid repeat units derived, as (B) repetitive by compound deriving with carboxylic acid ester groups, be preferably the repetitive of following general formula (II) expression, the repetitive of more preferably following general formula (IV) expression is preferably especially by the acrylic acid benzyl ester, the methacrylic acid benzyl ester, phenylethyl, the methacrylic acid phenethyl ester, acrylic acid 3-phenyl propyl ester or methacrylic acid 3-phenyl propyl ester repeat units derived.

General formula (I)

(R ₁Expression hydrogen atom or carbon number are 1～5 alkyl.)

General formula (II)

(R ₂Expression hydrogen atom or carbon number are 1～5 alkyl.R ₃Represent the group shown in the following general formula (III).)

General formula (III)

(R ₄Expression hydrogen atom, carbon number are that 1～5 alkyl, hydroxyl, carbon number are that 1～5 hydroxyalkyl or carbon number are 6～20 aryl.R ₅And R ₆Represent that respectively hydrogen atom or carbon number are 1～5 alkyl.I represents 1～5 number.)

General formula (IV)

(R ₇Expression hydrogen atom or carbon number are 1～5 alkyl.R ₈Represent the group shown in the following general formula (V).)

General formula (V)

(R ₉The expression carbon number is that 2～5 alkyl or carbon number are 6～20 aryl.R ₁₀And R ₁₁Represent that respectively hydrogen atom or carbon number are 1～5 alkyl.J represents 1～5 number.)

In addition, with regard to (A) by the repetitive of compound deriving with (B) with regard to the polymerization ratio of the repetitive of compound deriving with carboxylic acid ester groups with carboxyl, repetitive (A) is preferably 3～40 with respect to the quantity of whole number of repeat unit than %, and more preferably 5～35.

Among the present invention, if do not specify, the high molecular molecular weight in the manufacture method of the present invention is meant the quality mean molecular weight.As the assay method of high molecular molecular weight, can enumerate chromatography, viscosimetry, light scattering method, sedimentation velocity method etc.In the present invention, if do not specify, all be by gel permeation chromatography (carrier: tetrahydrofuran) measure and through the quality mean molecular weight of polystyrene conversion.

Macromolecular compound can be any in water-soluble, the oil-soluble, also can be water-soluble and oil-soluble.

The addition manner of macromolecular compound can be that macromolecular compound is dissolved in the solution that forms in aqueous solvent or the organic solvent, also can be solid state, in addition, also can be their combination.Be dissolved in the method that the solution that forms in the solvent adds as employing, for example can enumerate being dissolved in the solvent identical, add the method in the organic filler liquid of aggegation with this state to the solvent of the organic filler liquid of aggegation; Be dissolved in the solvent miscible but different, add the method in the organic filler liquid of aggegation with this state to the solvent of the organic filler liquid of aggegation.Employing is dissolved in the solution that forms in the solvent when adding, and the concentration of macromolecular compound is not particularly limited, but is preferably 1～70 quality %, and more preferably 2～65 quality % are preferably 3～60 quality % especially.

The interpolation of macromolecular compound can be following random time: the separating out when generating or when before and after it, when concentrating or before and after it, after concentrating the organic filler of cohesion being disperseed or before and after it, after these operations finish, also can divide in addition several times and add of pigment particle.In manufacture method of the present invention, can make also that to contain the quality mean molecular weight in the following composition as cementing agent be macromolecular compound more than 1000, for example preferably after the pigment particle lye concentrates, when making the organic filler fine dispersion of aggegation, add.

When pigment particle was made as 100 mass parts, the addition of macromolecular compound was preferably 0.1～1000 mass parts, and more preferably 5～500 mass parts are preferably 10～300 mass parts especially.

As molecular weight is macromolecular compound more than 1000, except that above-claimed cpd, for example can enumerate part butyral thing, vinyl pyrrolidone-vinyl acetate co-polymer, polyethylene oxide/propylene oxide segmented copolymer, polyamide, cellulose derivative, starch derivative of part formolation thing, the polyvinyl alcohol (PVA) of polyvinyl pyrrolidone, polyvinyl alcohol (PVA), polyvinyl methyl ether, polyethylene oxide, polyglycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate co-polymer, polyvinyl alcohol (PVA) etc.In addition, can also use natural polymers such as alginate, gelatin, albumin, casein, Arabic gum, bassora gum (ト Application ガ Application ト go system), lignosulfonate.As macromolecular compound, can enumerate poly-sulfuric acid vinyl ester, condensation naphthalene sulfonic acids etc. with acidic-group.

As macromolecular compound, for example can enumerate polyacrylic acid, polymethylacrylic acid, side chain and have cellulose derivative of carboxyl etc. with carboxyl.As containing (A), can enumerate communique such as Japanese kokai publication sho 59-44615 by at least a the reaching in the repetitive of compound deriving (B) by at least a copolymerization in the repetitive of compound deriving with carboxylic acid ester groups with carboxyl, the spy opens clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, the spy opens clear 59-53836 communique and the special methacrylic acid copolymer of putting down in writing in the clear 59-71048 communique of opening, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, maleic acid, the maleic acid of partial esterification etc.In addition, as more preferred example, can enumerate acrylic acid and acrylic ester copolymers, methacrylic acid-acrylate copolymer, acrylic acid-methacrylate copolymer, methacrylic acid-methacrylate copolymer, acrylic or methacrylic acid and the acrylate put down in writing in No. 4139391 instructions of United States Patent (USP) or the multiple copolymer of methacrylate and other vinyl compound.

As the example of vinyl compound, can enumerate vinyl naphthalene, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile of styrene (for example vinyltoluene, vinyl ethylbenzene), vinyl naphthalene or the replacement of styrene or replacement etc.Optimization styrene.

Molecular weight is that the macromolecular compound more than 1000 can only be used singly, or in combination of two or more kinds, and also can also use with the compound of molecular weight less than 1000.

Above-mentioned pigment particle disperses preferably to contain the above organic solvent of 60 quality % in the thing, more preferably more than the 65 quality %.There is no particular limitation to this organic solvent, can suitably select from common solvent.For example preferred ester compounds solvent, alcoholic compound solvent, aromatic compound solvent, fatty compound solvent, ketonic compound solvent, preferred especially ester compounds solvent, ketonic compound solvent.These solvents can use a kind separately, also can use simultaneously more than 2 kinds.

As the ester compounds solvent, for example can enumerate 2-(1-methoxyl) propyl group acetate, ethyl acetate, ethyl lactate etc.As the alcoholic compound solvent, for example can enumerate normal butyl alcohol, isobutyl alcohol etc.As aromatic compound solvent, for example can enumerate benzene,toluene,xylene etc.As the fatty compound solvent, for example can enumerate normal hexane, cyclohexane etc.As the ketonic compound solvent, for example can enumerate MEK, acetone, cyclohexanone etc.

Above-mentioned pigment particle can use with the state that for example is scattered in the carrier.As above-mentioned carrier, coating is meant the medium part that makes pigment dispersing when being in liquid condition, comprise aqueous the combination with above-mentioned pigment and part (cementing agent) that set is filmed and it is carried out the composition (organic solvent) of dissolved dilution.Also have, in the present invention, the cementing agent that uses when forming nano particle and disperse again in the cementing agent that uses can be identical or different, be will form the cementing agent that the cementing agent of nano particle reaches when disperseing again to distinguish sometimes.

Pigment particle concentration after can coming suitably to determine to disperse again according to purpose in the pigment particle dispersive composition, but the preferred pigments particulate is 2～30 quality % with respect to the total amount of dispersive composition, more preferably 4～20 quality % are preferably 5～15 quality % especially.Under the situation of utilizing carrier to disperse as mentioned above, the amount of cementing agent and dissolved dilution composition can suitably be selected according to organic pigment kind etc., with respect to the dispersive composition total amount, cementing agent is preferably 1～30 quality %, more preferably 3～20 quality % are preferably 5～15 quality % especially.The dissolved dilution composition is preferably 5～80 quality %, more preferably 10～70 quality %.

For the nano particle liquid after the above-mentioned concentration extraction, as previously mentioned, become possibility in order to make filtrator filtration fast, preferably make the pigment particle aggegation by concentrating, preferably concentrate and make its aggegation by centrifuging or drying.

As making this aggegation nano particle carry out the method for fine dispersion, for example can adopt ultrasonic scattering method and apply the method for physical energy.

Employed ultrasonic irradiation device preferably has can apply the above hyperacoustic function of 10kHz, for example can enumerate ultrasonic homogenizer, supersonic wave cleaning machine etc.If the liquid temperature rises during ultrasonic irradiation, then can cause the thermal thermocoagulation (referring to non-patent literature 1) of nano particle, therefore preferred liquid temperature is 1～100 ℃, more preferably 5～60 ℃.As temperature-controlled process, can be by control dispersion liquid temperature, the adjustment layer of control dispersion liquid temperature is carried out temperature control and implement.

To as applying the dispersion machine that uses when physical energy disperses pigment particle after concentrating, be not particularly limited, for example can enumerate dispersion machines such as kneader, roll crusher, second reduction machine (アトライダ-), high-speed grinder, dissolving machine, homo-mixer, sand mill.In addition, can also enumerate the high pressure dispersion method, and by using method that microballon disperses as method for optimizing.

According to above-mentioned manufacture method, for example for contained pigment particles in pigment particle dispersive composition or the photosensitive composition described later, although be that (for example 10～100nm) nominal particle size also can concentrate and disperse so-called nano-scale.Therefore, when being used for color filter, the excellent in uniformity on its optical concentration height, color filter surface, contrast height, and reduced picture noise.

And, can make pigment particle contained in pigment particle dispersive composition, the coloring photosensitive combination carry out height or fine equably dispersion, therefore, for example can make color filter etc. realize thin layerization than also bringing into play the brilliant idea colour saturation under the minimal thickness.

For pigment particle dispersive composition, coloring photosensitive combination, by it being contained demonstrate distinct color and high-strength pigment, it is excellent as being used to make the Image forming material that color filter for example or color draw a design.

And; exposure during for the formation rendered image, the alkaline-based developer that uses when developing; can use the material that dissolves in alkaline aqueous solution as cementing agent (binder) in pigment particle dispersive composition, coloring photosensitive combination, this also meets the needs of environmental protection.

In addition,, can use organic solvent with appropriate drying property as the solvent that uses in pigment particle dispersive composition, the coloring photosensitive combination (dispersing of pigments medium), from the coating after drying, this requirement also is satisfiable.

[ink-jet ink for color filter]

Used ink-jet ink in the color filter of the present invention (below be called " ink-jet ink for color filter of the present invention ") preferably contains (a) separates out pigment particle and (b) polymerizable monomer and/or polyreactive oligomers, more preferably contain (a) and separate out pigment particle, (b) polymerizable monomer and/or polyreactive oligomers, (c) cementing agent and (d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system, further preferably contain (1) have cementing agent (A) down being dissolved in the good solvent and the pigment solution that forms and with the pigment particle of separating out that makes after poor solvent that this solvent mixes mixes this pigment with the form generation of particulate, (2) cementing agent (B), (3) monomer or oligomer and (4) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.(A) Yu (B) can be the same or different.Below above-mentioned (a)～(d) of ink-jet ink for color filter of the present invention become to grade and describe.

(a) pigment particle

Method for making about pigment particle is described in detail.The content of pigment particle, with respect to whole solid contents of ink-jet ink for color filter (in the present invention, all solid contents are meant the component total except that organic solvent) be preferably 3～90 quality %, more preferably 20～80 quality %, more preferably 25～60 quality %.If should measure too much, then the concentration of dispersion liquid rises, and causes making the problem on the adaptability sometimes.If very few, colouring power deficiency then.As the pigment particle with colorant function, particle diameter is preferably below the 0.1 μ m, and special preferable particle size is below the 0.08 μ m.In addition, also can be used in combination with the common pigments that is used to mix colours.Can use above-described organic pigment kind as pigment.

(b) polymerizable monomer and/or polyreactive oligomers

Polymerizable monomer and/or polyreactive oligomers contained in the ink-jet ink for color filter of the present invention are preferably the ethylenical unsaturated double bonds that has more than 2, and can carry out the monomer or the oligomer of addition polymerization by illumination.As this monomer or oligomer, can enumerate and have at least one ethylenically unsaturated group that can carry out addition polymerization, the boiling point under the normal pressure in the molecule at the compound more than 100 ℃.As its example, can enumerate monofunctional acrylate or simple function methacrylates such as dipentaerythritol six (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; 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 (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) isocyanuric acid ester, three (acrylyl oxy-ethyl) cyanurate, glycerine three (methyl) acrylate; Polyfunctional alcohol such as trimethylolpropane or glycerine goes up polyfunctional acrylic ester or the multifunctional methacrylates such as material that forms through (methyl) acroleic acid esterification again behind addition of ethylene oxide or the epoxypropane.In addition, the general formula (1) that can also enumerate as Japanese kokai publication hei 10-62986 communique reaches those compounds that form through (methyl) acroleic acid esterification again of record in (2) as suitable material behind addition of ethylene oxide on the polyfunctional alcohol or epoxypropane.

These polymerizable monomers and/or polyreactive oligomers preferred molecular weight are 200～1000, can use separately, or mix more than 2 kinds and use, this monomer or oligomer are generally 5～50 quality % with respect to the content of whole solid contents of ink-jet ink for color filter, are preferably 10～40 quality %.If should measure too much, then be difficult to control development, can on manufacturing adaptability, have problems.If very few, the curing power deficiency when then exposing.

(c) cementing agent

That uses when decentralized again decentralizedly more preferably contains acidic-group with cementing agent, cementing agent described in preferred use above-mentioned " cementing agent " item, preferably form the compound that has similar structures with the alkali-soluble cementing agent with the pigment particle that is added when pigment particle forms, most preferably these two is identical.The decentralized again content with the alkali-soluble cementing agent (is having pigment particle to form under the situation of using the alkali-soluble glue residue, also can be the total content of these two cementing agent) be generally 15～50 quality % with respect to whole solid contents of ink-jet ink for color filter, be preferably 20～45 quality %.If should measure too much, then the viscosity of composition is too high, makes on the adaptability and can have problems.If very few, then having problems aspect the formation coated film.

(d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system

(in the present invention, the Photoepolymerizationinitiater initiater system is meant to be combined by multiple compound and realizes that photopolymerization causes the potpourri of function as the Photoepolymerizationinitiater initiater that contains in ink-jet ink for color filter of the present invention or Photoepolymerizationinitiater initiater system.), can enumerate disclosed vicinal polyketaldonyl compound in No. 2367660 instructions of United States Patent (USP), the acyloin ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series acyloin compound that the α that puts down in writing in No. 2722512 instructions of United States Patent (USP)-hydrocarbon replaces, 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 dipolymer of putting down in writing in No. 3549367 instructions of United States Patent (USP) and to the combination of amino ketones, benzothiazole compound of putting down in writing in the Japanese Patent Publication 51-48516 communique and trihalomethyl-s-triaizine compounds, trihalomethyl-triaizine compounds of putting down in writing in No. 4239850 instructions of United States Patent (USP), the San halogen Jia oxadiazole compound of putting down in writing in No. 4212976 instructions of United States Patent (USP) etc.Preferred especially trihalomethyl-s-triazine, San halogen Jia oxadiazole and triarylimidazoles dipolymer.

In addition; can also enumerate " the polymerization initiator C " that put down in writing in the Japanese kokai publication hei 11-133660 communique; and as the 1-phenyl-1 of oximes; 2-propanedione-2-(adjacent carbethoxyl group) oxime, O-benzoyl-4 '-(thiophenyl) benzoyl-hexyl-ketoxime, 2; 4,6-trimethylphenyl carbonyl-diphenylphosphine acyl-oxygen, hexafluorophosphoric acid-trialkyl Ben phosphonium salt etc. are as preferred material.

With respect to ink-jet ink for color filter, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.If should measure too much, then susceptibility is too high, is difficult to control.If very few, then exposure sensitivity is low excessively.

(other adjuvant)

[solvent]

In ink-jet ink for color filter of the present invention, except that mentioned component, in addition can also be with an organic solvent.To as representative examples of organic, be not particularly limited, can enumerate the ester class, for example ethyl acetate, n-butyl acetate, isobutyl acetate, the formic acid pentyl ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the hydroxacetic acid methyl esters, the hydroxacetic acid ethyl ester, the hydroxacetic acid butyl ester, Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the ethoxy methyl acetate, the ethoxy ethyl acetate, the 3-hydroxy methyl propionate, 3-hydracrylic acid alkyl esters such as 3-hydracrylic acid ethyl ester; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, the 2-beta-hydroxymethyl butyrate, 2-3-hydroxyethyl butyrate etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methyl cellosolve, acetic acid ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate etc.; Ketone, for example MEK, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone etc.; Arene, for example toluene, dimethylbenzene etc.In these solvents, preferably use 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetic acid ethyl cellosolve, ethyl lactate, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate etc. as the solvent among the present invention.These solvents can use separately or organize more than 2 kinds and close use.

The content of solvent is preferably 10～95 quality % with respect to the ink-jet ink for color filter total amount.

[surfactant]

The color filter of Shi Yonging in order to realize high color purity, need make each color of pixel enriching in the past, and people recognize and do the following problem that exists like this that promptly the membrane thickness unevenness of pixel causes color inhomogeneous.Therefore, need improve at the Thickness Variation that the pixel film thickness is had a direct impact.

For color filter of the present invention, from controlling uniform thickness, effectively preventing because the uneven viewpoint of color that Thickness Variation causes preferably makes and contains suitable surfactant in the ink-jet ink for color filter.

As above-mentioned surfactant, can enumerate TOHKEMY 2003-337424 communique, spy and open in the flat 11-133600 communique disclosed surfactant as the surfactant that is fit to.With respect to the ink-jet ink for color filter total amount, the content of surfactant is preferably below the 5 quality %.

[thermal polymerization prevents agent]

Preferably contain thermal polymerization in the ink-jet ink for color filter of the present invention and prevent agent.Prevent the example of agent as this thermal polymerization, can enumerate quinhydrones, Hydroquinone monomethylether, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-sulphur two (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, phenothiazine etc.With respect to the ink-jet ink for color filter total amount, thermal polymerization prevents that the content of agent is preferably below the 1 quality %.

[auxiliary dyestuff, the pigment that uses]

In case of necessity, in ink-jet ink for color filter of the present invention, in the scope of not damaging effect of the present invention, except that above-mentioned colorant (pigment), can add colorant (dyestuff, pigment).When using the pigment in the colorant, preferably make it in ink-jet ink for color filter, reach even dispersion, so its particle diameter is preferably below the 0.1 μ m, below 0.08 μ m.

As dyestuff or pigment, specifically, be fit to use the coloured material of putting down in writing in [0038]～[0040] of TOHKEMY 2005-17716 communique as above-mentioned pigment, the spy opens the pigment of record in 2005-361447 communique [0068]～[0072], and the special colorant of putting down in writing in [0080]～[0088] of 2005-17521 communique of opening.With respect to the ink-jet ink for color filter total amount, the auxiliary dyestuff that uses or the content of pigment are preferably below the 5 quality %.

[ultraviolet light absorber]

In case of necessity, can contain ultraviolet light absorber in the ink-jet ink for color filter of the present invention.As ultraviolet light absorber, the compound of in Japanese kokai publication hei 5-72724 communique, putting down in writing, also can enumerate salicylate class, benzophenone, benzotriazole, cyanoacrylate, nickel chelate class, hindered amines etc.

Specifically, can enumerate the salicylic acid phenylester, 4-tert-butyl-phenyl salicylate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, 4-tert-butyl-phenyl salicylate, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-cyano group-3, the 3-diphenyl-ethyl acrylate, 2,2 '-hydroxyl-4-methoxy benzophenone, nickel dibutyl dithiocarbamate, two (2,2,6,6-tetramethyl-4-pyridine)-sebacate, 4-tert-butyl-phenyl salicylate, the salicylic acid phenylester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation product, succinic acid-two (2,2,6,6-tetramethyl-4-piperidyl)-ester, 2-[2-hydroxyl-3, two (α, the α-Er Jiajibianji) phenyl of 5-]-the 2H-benzotriazole, 7-{[4-chloro-6-(lignocaine)-5-triazine-2-yl] amino }-3-phenyl cumarin etc.With respect to the ink-jet ink for color filter total amount, the content of ultraviolet light absorber is preferably below the 5 quality %.

In addition, except that above-mentioned adjuvant, can also contain " adhesive aid " put down in writing in the Japanese kokai publication hei 11-133600 communique and other adjuvant etc. in the ink-jet ink for color filter of the present invention.

In ink-jet ink for color filter of the present invention, preferably the temperature of ink is controlled, so that its viscosity amplitude of variation is in ± 5%.Viscosity during injection be preferably 5～25mPas, more preferably 8～22mPas, be preferably 10～20mPas (viscosity number when unless otherwise specified, viscosity described in the present invention is 25 ℃) especially.Except by setting above-mentioned injection temperation, also can regulate viscosity by the kind and the addition of regulating ingredient in the ink.Described viscosity for example can adopt usual means such as cone-plate type rotational viscosimeter or E type viscosity meter to measure.

Consider that from the flatness aspect that improves pixel the surface tension of ink is preferably 15～40mN/m (unless otherwise specified, the value when surface tension described in the present invention is 23 ℃) during injection, more preferably 20～35mN/m, most preferably be 25～30mN/m.Can come the reconciliation statement surface tension by adding surfactant or changing solvent types.Described surface tension for example can be utilized surface tension apparatus (the CBVP-Z type that consonance Surface Science Co., Ltd. makes) or full automatic balance type electron surface tensiometer ESB-V known determining instruments such as (consonance Surface Science Co., Ltd. make), adopts platinum plate method to measure.

[the color filter injection of spraying ink]

As the injection method of ink-jet ink for color filter of the present invention, the whole bag of tricks such as method that method, the heating ink that can adopt charged ink of continuous injection and the method for being controlled by electric field, intermittently sprays ink with piezoelectric element utilizes its foaming intermittently to spray.

Used ink ejecting method when forming each pixel can adopt the method that makes the ink heat curing, makes the method for ink photocuring, form transparent image receiving layer in advance on substrate and water the common methods such as method of dripping then.

Ink gun (following also abbreviate as " shower nozzle ") can use ink gun commonly used, can use continuous injection type, need based jet type (dot on demand).In the need based jet type, aspect temperature-sensitive shower nozzle (thermal head), in order to spue, preferably as the sort of temperature-sensitive shower nozzle described in the Japanese kokai publication hei 9-323420 communique with operating valve.Aspect piezo jets, the shower nozzle described in for example can use European patent A 277, No. 703,278, No. 590 grades of European patent A.The shower nozzle that preferably has temp regulating function is so that can control the temperature of ink.Set injection temperation so that the viscosity when spraying is 5～25mPas, preferably ink temperature is controlled so that spread of viscosity in ± 5%.In addition, preferably carry out work with the driving frequency of 1～500kHz.

After each pixel forms, the heating process of heat treated (so-called cure processing) can be set.That is, will have the substrate that photopolymerisable layer is taken place by rayed is placed on and heats in electric furnace, the exsiccator etc. or shine with infrared lamp.The temperature and time of heating depends on the composition of photonasty heavy colour composition and the thickness of formed layer, generally consider, be preferably at about 120 ℃～about 250 ℃ and heated about 10 minutes～about 120 minutes down from obtaining sufficient solvent resistance, alkali resistance and UVA degree aspect.

Pattern form to formed color filter does not thus limit especially, its can for the bar shaped of general black matrix (black matrix) shape, also can be for grid shape, can also be the shape of rounded projections arranged.

Preferably, among the present invention, before forming the operation of pixel, make the next door in advance, sprayed the such method for making of ink by the part that this next door surrounded with above-mentioned ink-jet ink for color filter.Though described next door can be any material, when making color filter, preferably, has the next door (following also abbreviate as " next door ") of the light-proofness of black matrix function.Can adopt with color filter commonly used and make this next door with black matrix identical materials, method.For example in the TOHKEMY 2005-3861 communique in [0021]～[0074] section, TOHKEMY 2004-240039 communique in the black matrix described in [0012]～[0021] section or the TOHKEMY 2006-17980 communique in [0015]～[0020] section, TOHKEMY 2006-10875 communique the ink-jet described in [0009]～[0044] section with black matrix etc.

＜liquid crystal indicator 〉

Liquid crystal indicator of the present invention uses the color filter of contrast excellence of the present invention, and the black density of liquid crystal indicator of the present invention etc. is described the power excellence.Also be suitable as notebook computer with the liquid crystal indicator of big picture such as display and TV monitor etc.

About liquid crystal indicator, for example be recorded in " inferior generation liquid crystal デイスプレイ technology (Uchida Tatsuo compiles, the meeting of (strain) census of manufacturing, distribution in 1994) ".The applicable liquid crystal indicator of ink-jet ink for color filter of the present invention, color filter and manufacture method thereof is not particularly limited, for example goes for the liquid crystal indicator of the variety of way of record in above-mentioned " inferior generation liquid crystal デイスプレイ technology ".Wherein, effective especially for the liquid crystal indicator of colored TFT mode.Liquid crystal indicator about colored TFT mode for example is recorded in " カラ-TFT liquid crystal デイスプレイ (upright publication (strain) altogether, distribution in 1996) ".In addition, also be applicable to the liquid crystal indicator that the angle of visibility of pixel partitioning schemes such as horizontal component of electric field type of drive, MVA such as ISP etc. obtains enlarging.About these modes, for example be recorded in " EL, PDP, LCD デイスプレイ-technology and the up-to-date trend in market-(eastern レリサ-チセ Application -investigation department, calendar year 2001 distribution) " the 43rd page.

Except color filter, liquid crystal indicator is ensured by electrode substrate, polarizing coating, phase shift films, backlight, dottle pin, angle of visibility that also various parts such as film constitute.Black matrix of the present invention is applicable to the liquid crystal indicator that is made of these common components.About these parts, for example be recorded in " ' 94 liquid crystal デイスプレイ periphery material ケミカ Le ズ markets (the island Itou Kentaro; (strain) シ-エ system シ-; distribution in 1 994 years) ", " 2003 liquid crystal connections market status と looks forward to (last volume) (table is good lucky; the キメラ of (strain) Fuji combines and grinds, the calendar year 2001 distribution) in the future ".Herein, liquid crystal indicator of the present invention is preferably the VA mode.

[CCD device]

CCD device of the present invention has above-mentioned color filter.Below, CCD device of the present invention is elaborated.

Alkali soluble resins

As the alkali soluble resins that uses in the CCD device, preferably as the wire organic high molecular polymer, dissolve in organic solvent and can develop with weak base aqueous solution those.As such wire organic high molecular polymer, there is side chain to have the polymkeric substance of carboxylic acid, for example open maleic acid that clear 59-53836 number, spy open the methacrylic acid copolymer put down in writing in the clear 59-71048 instructions, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification etc., also have the acid cellulose derivant that on side chain, has carboxylic acid equally in addition such as Japanese kokai publication sho 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 number, special public clear 54-25957 number, spy.In addition, it also is useful having the material that forms behind the addition acid anhydrides on the polymkeric substance of hydroxyl.(methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer in preferred especially these materials, and the multiple copolymer of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid and other monomer.As other water-soluble polymers, can also use methacrylic acid 2-hydroxyl ethyl ester, polyvinyl pyrrolidone or polyethylene oxide, polyvinyl alcohol (PVA) etc.

In addition, can also enumerate in Japanese kokai publication hei 7-140654 number the big monomer of (methyl) acrylic acid 2-hydroxypropyl acrylate/polystyrene/methacrylic acid benzyl ester/methacrylic acid copolymer, the big monomer of 2-hydroxyl-3-phenoxy propyl acrylate/polymethylmethacrylate/methacrylic acid benzyl ester/methacrylic acid copolymer, the big monomer/methyl methacrylate of methacrylic acid 2-hydroxyl ethyl ester/polystyrene/methacrylic acid copolymer, the big monomer of methacrylic acid 2-hydroxyl ethyl ester/polystyrene/methacrylic acid benzyl ester/methacrylic acid copolymer etc. of record.As the addition of above-mentioned alkali soluble resins in solidification compound, be 5～90 quality % preferably with respect to the composition gross mass, 10～60 quality % more preferably.

Polymerizable monomer

As polymerizable monomer, preferably has the compound that at least one can carry out the vinyl of addition polymerization, has the boiling point more than 100 ℃ under normal pressure with ethylenically unsaturated group.

As having at least one vinyl that can carry out addition polymerization, boiling point, can enumerate monofunctional acrylate or methacrylates such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) phenoxyethyl acrylate under the normal pressure being compound more than 100 ℃; Polyglycol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, neopentyl glycol two (methyl) acrylic acid, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, hexanediol (methyl) acrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) isocyanuric acid ester, polyfunctional alcohol such as glycerine or trimethylolethane goes up the material that forms through (methyl) acroleic acid esterification again behind addition of ethylene oxide or the epoxypropane, special public clear 48-41708 number, special public clear 50-6034 number, the spy opens the sort of urethane acrylate class of putting down in writing in clear 51-37193 number each communique, the spy opens clear 48-64183 number, special public clear 49-43191 number, the polyester acrylate class of putting down in writing in special public clear 52-30490 number each communique, polyfunctional acrylic ester or methacrylates such as epoxy acrylate class as epoxy resin and (methyl) acrylic acid resultant of reaction.In addition, can also use then Xie Hui Chi Vol.20 of Japan, No.7, the material of introducing as photo-curable monomer and oligomer in 300～308 pages.

In addition, can also use following general formula (B-1) or (B-2) shown in compound.

General formula (B-1)

General formula (B-2)

{ among general formula (B-1), (B-2), B represents-(CH independently of one another ₂CH ₂O)-and-(CH ₂CH (CH ₃) O)-in any group; X represents any group in acryloyl group, methacryl and the hydrogen atom independently of one another, and, acryloyl group in the formula (B-1) and methacryl add up to 5 or 6, it is 3 or 4 in formula (B-2); N represents 0～6 integer independently of one another, and each n add up to 3～24; M represents 0～6 integer independently of one another, and each m add up to 2～16.}

As these polymerizable monomers, have filming of cementability if can form when being subjected to radiation exposure, then can use with arbitrary proportion.With respect to whole solid contents of composition, the use amount of this monomer is generally 5～90 quality %, is preferably 10～50 quality %.

Colorant

As colorant, can use a kind of in known in the past dyestuff, inorganic pigment or the organic pigment or be mixed with two or more.

There is no particular limitation to dyestuff, can use the known dyestuff that in the past was used for color filter.For example, can use disclosed pigment in Japanese kokai publication sho 64-90403 communique, Japanese kokai publication sho 64-91102 communique, Japanese kokai publication hei 1-94301 communique, Japanese kokai publication hei 6-11614 communique, No. 2592207, patent registration, No. 4808501 instructionss of United States Patent (USP), No. 5667920 instructionss of United States Patent (USP), No. 505950 instructionss of United States Patent (USP), No. 5667920 instructionss of United States Patent (USP), Japanese kokai publication hei 5-333207 communique, Japanese kokai publication hei 6-35183 communique, Japanese kokai publication hei 6-51115 communique, the Japanese kokai publication hei 6-194828 communique etc.As chemical constitution, can use dyestuffs such as pyrazoles azo class, anilino-azo class, triphenylmethane, anthraquinone class, benzal class, Oxonol class, pyrazoles triazole azo class, pyridinone, cyanine class, phenothiazines, pyrrolo-pyrazoles azomethine class.Especially, because solidification compound can solidify at a lower temperature,, also can alleviate the problems such as decomposition that back baking high temperature following time of being used to give the cured film permanance occurs that are exposed to even therefore thermotolerance is than the dyestuff of pigment difference.

As inorganic pigment is the metallic compound of representing with metal oxide, metallic complex salt etc., specifically, can enumerate the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc., and the composite oxides of above-mentioned metal.

As organic pigment, can enumerate C.I. pigment yellow 11,24,31,53,83,85,99,108,109,110,138,139,150,151,154,167,185, C.I. pigment orange 36,38,43,71, C.I. paratonere 105,122,149,150,155,171,175,176,177,209,224,242,254, C.I. pigment violet 19,23,32,39, C.I. pigment blue 1,2,15,16,22,60,66,15:3,15:6, C.I. pigment Green 7,36,37, C.I. pigment brown 25,28, C.I. pigment black 1,7, carbon black etc.

These organic pigments can use separately, or carry out various being used in combination in order to improve excitation.Concrete example is as follows.As red, can use anthraquinone class pigment, perylene class pigment separately, or use at least a and bisdiazo class yellow uitramarine in them or the mixing of isoindoline class yellow uitramarine.For example, as anthraquinone class pigment, can enumerate C.I. paratonere 177, Zuo Wei perylene class pigment can be enumerated C.I. paratonere 155, and from the angle of colorrendering quality, it is good mixing with C.I. pigment yellow 83 or C.I. pigment yellow 13 9.The mass ratio of red pigment and yellow uitramarine is 100: 5 to 100: 50th, and is good.When being in this scope, can suppress the light transmission rate of 400nm～500nm, improve excitation, be preferred therefore.

As viridine green, can use halogenated phthalocyanines class pigment separately, or mix use with bisdiazo class yellow uitramarine, Kui phthalein ketone yellow uitramarine or isoindoline class yellow uitramarine, for example preferred C.I. pigment Green 7,36,37 and C.I. pigment yellow 83,138,139 mixing.The mass ratio of viridine green and yellow uitramarine is preferably 100: 5 to 100: 100.When being in this scope, can suppress the light transmission rate of 400nm～450nm, obtain good excitation.

As blue pigment, can use phthalocyanine pigment separately, or mix use, for example preferred C.I. pigment blue 15: 6 and the mixing of C.I. pigment Violet 23 Yu the dioxazines violet pigment.The mass ratio of blue pigment and violet pigment is preferably 100: 0 to 100: 50.When being in this scope, can suppress the light transmission rate of 400nm～420nm, improve excitation.

In addition, by using, can obtain to contain the photosensitive polymer combination of the good pigment of dispersiveness and dispersion stabilization with the fine Powdered processed pigment that forms in acrylic resin, maleic acid resinoid, vinyl chloride-vinyl acetate copolymer and the ethyl cellulose resin etc. that is scattered in of above-mentioned pigment.

In addition, as the pigment that uses in the black matrix, can use separately or mix and use carbon, titanium dioxide, iron oxide, the situation of carbon and titanium dioxide be used in preferred mixing.The mixing quality ratio is preferably 100: 5 to 100: 40.When being in this scope, long wavelength's light transmission rate is low, also has good dispersion stabilization in addition.

Solvent

As solvent, can enumerate the ester class, for example 3-hydracrylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, formic acid pentyl ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxacetic acid methyl esters, hydroxacetic acid ethyl ester, hydroxacetic acid butyl ester, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, ethoxy methyl acetate, ethoxy ethyl acetate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, the 2-beta-hydroxymethyl butyrate, 2-3-hydroxyethyl butyrate etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methyl cellosolve, acetic acid ethyl cellosolve, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, propylene glycol methyl ether acetate, propylene glycol ethylether acetate, propylene glycol propyl ether acetate etc.; Ketone, for example MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.; Arene, for example toluene, dimethylbenzene etc.

In these solvents, preferably use 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetic acid ethyl cellosolve, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate etc.In composition, the addition of solvent is generally 60～90 quality %, is preferably 70～90 quality %.

These solvents can use separately or be used in combination more than 2 kinds.

Can also and use sensitizer.As its object lesson, can enumerate 9-Fluorenone, 2-chloro-9-Fluorenone, 2-methyl-9-Fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, the 2-tert-butyl group-9,10-anthraquinone, 2,6-two chloro-9,10-anthraquinone, benzil, dibenzalacetone, right-(dimethylamino) styryl phenyl base ketone, right-(dimethylamino) phenyl-p-methylstyrene base ketone, benzanthrone etc., and the benzothiazole compound of putting down in writing in the Japanese Patent Publication 51-48516 communique.

Can use various mixers, dispersion machine to above-mentioned principal ingredient and other adjuvant mixing dispersion of use in case of necessity, thereby be prepared.

The general manufacture method of the color filter that uses in the CCD device is as follows.Carry out coating composition of the present invention (colored resist liquid) on the substrate successively and carry out dry operation, the operation, exposure back of carrying out pattern exposure with i line stepping exposure machine be with the operation of alkali development, carry out the operation of heat treated then, repeat above-mentioned operation in turn for shades of colour (3 looks or 4 looks), make cured film, thereby obtain color filter.

More particularly, utilize spinner to be coated with above-mentioned solidification compound on suitable substrate, the thickness when making drying is generally 0.1～5 μ m, is preferably 0.2～2 μ m, places 2 minutes in 85 ℃ baking oven, is smoothly filmed.

There is no particular limitation to substrate, can enumerate glass plate, plastic plate, aluminium sheet, imaging apparatus with substrate for electronic component such as silicon chips, and transparent resin plate, resin molding, the sensitive surface that is formed with Braun tube display surface, pick-up tube, CCD, BBD, the wafer of solid-state imagers such as CID, BASIS, the closing-type imageing sensor that has used thin film semiconductor, liquid crystal display face, color electronography are with the substrate of the display device of photoreceptor, エト Network トロ Network ロミイ-(EC) etc.In addition, preferably substrate is implemented to be used to improve itself and the high driving fit processing of the cementability of color-filter layer.Specifically, on substrate, carry out the thin layer coating with coupling agent etc. in advance, form solidification compound then, or make in advance and contain silane coupling agent in the solidification compound.

In addition, when on substrate, having difference in height, can on substrate, be coated with and be provided for eliminating difference in height, make the level and smooth planarization film of coated face, be coated with solidification compound of the present invention then.For example, imageing sensors such as CCD are made of the readout gate portion that produces the photoelectric conversion part (photodiode) of electronics according to light income and be used to export its electronics that produces on the organosilicon substrate, if but readout gate is subjected to light, then can cause noise, output data correctly, therefore the shading rete to be set on the top of readout gate portion, itself and do not have between the photodiode portion of shading rete and produce difference in height sometimes.If coating chromatic resist on this difference in height directly forms color filter, then optical path length becomes big, so image deepening or light harvesting variation.In order to improve this problem, preferably between CCD and color filter, form the transparent planarization film that purpose is the landfill difference in height.As the material of this planarization film, can enumerate thermoset resins such as the sort of photo-curable resist liquid among the present invention, acrylic compounds, epoxies etc.

Behind the coating Photocurable composition,, to carry out preliminary drying usually for evaporating solvent obtains dry coated film.As the method for preliminary drying, drying under reduced pressure is arranged, utilize high temperature air etc. to carry out the indirect heating drying, utilize electric furnace etc. to carry out direct drying (about 80～about 140 ℃, 50～200 seconds) etc.In addition, fully solidify, obtain the high permanent film of physical strength, need carry out the back baking in order to make the pattern that obtains after the development.For example, when making 3 look color filters, after this initial pattern that forms can stand coating, exposure, the development of other color resist liquid once more.At this moment, for fear of the pattern defect that colour mixture, exposure, development with the resist liquid that is coated with cause, carry out the back baking.The baking of this back can be used the method identical with preliminary drying, but will carry out under the temperature higher than prebake conditions, longer time.For example, utilizing baking oven to carry out under the situation of indirect heating, under about 180～about 250 ℃, carrying out about 0.5～about 2 hours, when utilizing electric furnace directly to heat, under about 180～about 250 ℃, carrying out about 2～about 10 minutes.

There is no particular limitation to the light source that is used to expose, but as for forming pattern the light source of remarkable result being arranged, can enumerate the i line of mercury vapor lamp.Consider that from the aspect that technology is suitable when use was used color filter as the i line construction drawing image-position sensor of one of mercury vapor lamp spectral line, feature of the present invention was remarkable especially, certainly, also can use for CCD.

The developer solution that uses when solidification compound is developed is not particularly limited, and can use known in the past developer solution.Wherein, organic bases developer solution of tetramethyl ammonium hydroxide quaternary ammonium salts such as (TMAH) can reach purpose of the present invention, is preferred therefore.

Polymerization initiator

As polymerization initiator, can use common Photoepolymerizationinitiater initiater.Specifically, can enumerate the vicinal polyketaldonyl compound of putting down in writing in No. 2367660 instructions of United States Patent (USP), the alpha-carbonyl compound of putting down in writing in No. the 2367661st, United States Patent (USP) and No. 2367670 instructions, the acyloin ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series acyloin compound that the α that puts down in writing in No. 2722512 instructions of United States Patent (USP)-hydrocarbon replaces, the polynucleation quinone compound of putting down in writing in No. 3046127 instructions of United States Patent (USP) and No. 2951758 instructions, the combination of triarylimidazoles dipolymer/p-aminophenyl ketone of putting down in writing in No. 3549367 instructions of United States Patent (USP), benzothiazole compound/trihalomethyl of putting down in writing in the Japanese Patent Publication 51-48516 communique-s-compound in triazine class etc.

Solid content (quality) with respect to free radical polymerization monomer, the content of Photoepolymerizationinitiater initiater (comprising above-mentioned common Photoepolymerizationinitiater initiater) in containing the minus solidification compound of dyestuff is preferably 0.01～50 quality %, more preferably 1～30 quality % is preferably 1～20 quality % especially.If this content is in the above-mentioned scope, then can carry out polymerizing curable fully, polymerization can not occur and be difficult to carry out, or aggregate rate raises and the molecular weight reduction situation that film strength weakens.

In addition, above-mentioned Photoepolymerizationinitiater initiater can and be used with sensitizer or light stabilizer.

As its object lesson, can enumerate benzoin, benzoin methyl ether, the 9-Fluorenone, 2-chloro-9-Fluorenone, 2-methyl-9-Fluorenone, the 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9, the 10-anthraquinone, 2-ethyl-9, the 10-anthraquinone, the 2-tert-butyl group-9, the 10-anthraquinone, 2,6-two chloro-9, the 10-anthraquinone, xanthone, 2-methyl xanthone, 2-methoxyl xanthone, 2-ethoxy xanthone, thioxanthones, 2, the 4-diethyl thioxanthone, acridone, 10-butyl-2-chloro-acridine ketone, benzil, dibenzalacetone, right-(dimethylamino) styryl phenyl base ketone, right-(dimethylamino) phenyl-p-methylstyrene base ketone, benzophenone, right-(dimethylamino) benzophenone (or michaelis ketone), right-(diethylamino) benzophenone, benzanthrone etc., and the benzotriazole compound of Japanese Patent Publication 51-48516 communique record etc., チヌ PVC Application 1130,400 etc.

[embodiment]

Below the present invention is described in detail based on embodiment, but the present invention is not limited thereto.

(embodiment 1 comparative example 1)

The preparation of＜pigment dispensing composition A 〉

[preparation of dispersible pigment dispersion]

In 2000ml dimethyl sulfoxide (DMSO) (producing) with the pure medicine of light Co., Ltd., add methanol solution, 100g pigment C.I. paratonere 254 (the Irgaphor RedBT-CF of the sodium methoxide 28% of 100.0ml, trade name, チバスペシヤ Le テイケミカ Le ズ (strain) makes) and 170.0g polyvinylpyrrolidone (K-30, trade name, produce with the pure medicine of light Co., Ltd.), be mixed with pigment solution A.Measure the viscosity of this pigment solution A with viscosity meter VM-10A-L (trade name, CBC マテリア Le ズ society make), the result is for when the temperature of pigment solution A is 25.0 ℃, and its viscosity is 18.4mPas.Simultaneously, prepare the water 2500ml that contains 1mol/l hydrochloric acid (with the pure medicine of light Co., Ltd. system) 16ml in addition as poor solvent.

At this moment, temperature is controlled to be 25 ℃, to utilizing GK-0222-10 type ラモ Application De ス -ラ-(trade name, rattan pool medicine society makes) among poor solvent-water 2500ml of stirring with the rotating speed of 500rpm, with NP-KX-500 type high capacity flexible hose pump (trade name, Japanese precision chemical society makes), be that the liquid pushing tube of 0.8mm injects 100ml pigment solution L by the flow velocity of 100ml/min from the stream diameter, thereby the formation organic pigment particles is made dispersible pigment dispersion A.Use Na ノトラ Star Network UPA-EX150 (trade name, day machine dress society makes) to measure number average bead diameter Mn and single dispersion degree (Mv/Mn) of this dispersible pigment dispersion, the Mn that records is 28nm, and Mv/Mn is 1.29.

For pigment nanoparticle dispersion liquid with method for preparing, the P89C type filter cloth that the H-122 type filter centrifugal made from コ Network サ Application Co., Ltd. and deposited island カ Application バス Co., Ltd. make, under 3000rpm, concentrate 100 minutes, reclaim resulting pigment nano particle and concentrate paste.

The 8453 type spectrophotometric determinations made from Agilent (Agilent) company concentrate the pigment containing ratio of sticking with paste, and the result is 15.9 weight %.After interpolation is synthesized the macromolecular compound 2.4g of the pigment dispersing agent A 0.3g, the compound example C-1 that obtain according to TOHKEMY 2000-239554 communique in the 50.0ml ethyl lactate, resulting solution is joined in the above-mentioned pigment nano particle preparation of the 15.0g paste, stirred 60 minutes under 1500rpm with dissolving machine, the FP-010 type filter made from the Off アイ of Sumitomo Electric Industries Application Port リマ society again after wherein adding the 25.0ml ethyl acetate filters, and concentrates pigment liquid A (nano dye concentration is 34.3 quality %) thereby obtain pasty state.

[preparation of pigment dispensing composition]

The pigment dispensing composition A that uses above-mentioned paste to prepare to have following composition.

Above-mentioned pasty state concentrates pigment liquid A 18.8g

1,3 butylene glycol diacetate 45.6g

Utilizing electronic mill M-50 (manufacturing of アイガ one ジヤパ Application Co., Ltd.), use the zirconia microballon of diameter as 0.65mm, is under the condition of 9m/s the pigment dispensing composition of above-mentioned composition to be disperseed 1 hour in peripheral speed.

The preparation of＜pigment dispensing composition B 〉

In the preparation of above-mentioned pigment dispensing composition A, the adding flow velocity except will add above-mentioned pigment solution A the time changes the 45ml/min other and the above-mentioned the same pigment dispensing composition B for preparing into.Measure number average bead diameter Mn and single dispersion degree (Mv/Mn), the Mn that records is 35nm, and Mv/Mn is 1.36.

The preparation of＜pigment dispensing composition C 〉

In the preparation of above-mentioned pigment dispensing composition A, the stream diameter of the liquid pushing tube except will add above-mentioned pigment solution A the time changes 2.20mm into, add flow velocity changes the 400ml/min other and the above-mentioned the same pigment dispensing composition C for preparing into.Measure number average bead diameter Mn and single dispersion degree (Mv/Mn), the Mn that records is 27nm, and Mv/Mn is 1.22.

The preparation of＜pigment dispensing composition D 〉

In the preparation of above-mentioned pigment dispensing composition A, the stream diameter of the liquid pushing tube except will add above-mentioned pigment solution A the time changes 0.25mm into, add flow velocity changes the 5ml/min other and the above-mentioned the same pigment dispensing composition D for preparing into.Measure number average bead diameter Mn and single dispersion degree (Mv/Mn), the Mn that records is 61nm, and Mv/Mn is 1.46.

The preparation of＜pigment dispensing composition E 〉

Following use Ball milling machine prepares the pigment dispensing composition E of following composition.

Pigment (paratonere 254) 6.43g

Pigment dispersing agent A 0.81g

Polyvinylpyrrolidone 10.90g

The macromolecular compound C-1 6.47g of example

Methacrylic acid/methacrylic acid benzyl ester multipolymer * 14.9g

( ^*Mol ratio 28/72, weight average molecular weight: 30,000,40% 1-methoxyl-2-propyl group acetic ester solution)

1,3 butylene glycol diacetate 35.80g

The preparation of＜pigment dispensing composition F 〉

The pigment dispensing composition F for preparing following composition according to following method.

Pigment (paratonere 254) 6.43g

Sodium chloride 64.0g

Pigment dispersing agent A 0.81g

The macromolecular compound C-1 6.47g of example

After in 1,3 butylene glycol diacetate liquid, adding the powder, methacrylic acid/methacrylic acid benzyl ester multipolymer of sodium chloride, pigment (paratonere 254), it is dosed in the both arms type mixer, mixed 6 hours down at 80 ℃.After the mixing, add 80 ℃ 1% aqueous hydrochloric acid solution, 500 weight portions, stir after 1 hour, filtration, hot water wash, drying, pulverizing add 2.4g 1,3 butylene glycol diacetate with respect to this crushed material of 1g then, mix.Utilizing electronic mill M-50 (manufacturing of アイガ one ジヤパ Application Co., Ltd.), use the zirconia microballon of diameter as 0.65mm, is under the condition of 9m/s above-mentioned color compositions to be disperseed 1 hour in peripheral speed.Obtain pigment dispensing composition F.

The preparation of＜pigment dispensing composition G 〉

In the preparation of above-mentioned pigment dispensing composition F, except incorporation time being changed into 20 hours, other same fully operation obtains pigment dispensing composition G.

The making of＜color filter 〉

[making of photosensitive transfer printing material]

At thickness is on the interim stilt of polyethylene terephthalate of 75 μ m, is coated with the thermoplastic resin coating fluid that is made of following prescription H1 with the slit-shaped nozzle, and carries out drying.Then, the middle layer coating fluid that coating is made of following prescription P1, and carry out drying.Be coated with the resin combination K1 that is constituted that forms again with light-proofness by record in the following table 1; and carry out drying; thereby the thermoplastic resin that dry film thickness is 15 μ m is set on this interim stilt, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the resin bed with light-proofness of 2.4 μ m, and pressing diaphragm (thickness is the polypropylene screen of 12 μ m).

Make the photosensitive resin transfer material that forms one by interim stilt, thermoplastic resin, middle layer (oxygen barrier layers) and resin bed with light-proofness thus, with this photosensitive resin transfer material sample called after K1.

^*Thermoplastic resin coating fluid: prescription H1

Methyl alcohol 11.1 mass parts

Propylene glycol monomethyl ether acetate 6.4 mass parts

MEK 52.4 mass parts

Methyl methacrylate/2-EHA/methacrylic acid benzyl ester/

Methacrylic acid copolymer

(copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8,

Molecular weight=100,000, about 70 ℃ of Tg) 5.83 mass parts

Styrene/acrylic acid co-polymer (copolymerization ratio of components (mol ratio)

=63/37, molecular weight=10,000, about 100 ℃ of Tg) 3.6 mass parts

2, two [4-(methacryloxypropyl polyethoxy) phenyl] propane (the Xin Zhong village chemical industry of 2-

(strain) system) 9.1 mass parts

Surfactant 1 0.54 mass parts

^*(メガ Off アッ Network F-780-F's (big Japanese ink chemical industry (strain) system) is composed as follows for surfactant 1

C ₆F ₁₃CH ₂CH ₂OCOCH=CH ₂: 40 mass parts,

H (OCH (CH ₃) CH ₂) ₇OCOCH=CH ₂: 55 mass parts and

H (OCH ₂CH ₂) ₇OCOCH=CH ₂: 5 mass parts

Multipolymer (molecular weight 30,000) 30 mass parts

MEK 70 mass parts

^*Fill a prescription with coating fluid in middle layer (oxygen barrier layers): P1

Polyvinyl alcohol (PVA) ... ... ... ... ... ... ... ... ... 32.2 mass parts

(PVA205 (saponification rate=88%); (strain) Network ラレ society system)

Polyvinyl pyrrolidone ... ... ... ... ... ... ... 14.9 mass parts

(PVP, K-30; アイエスピ-ジヤパ Application Co., Ltd. system)

Methyl alcohol ... ... ... ... ... ... ... ... ... ... the .429 mass parts

Distilled water ... ... ... ... ... ... ... ... ... ... the .524 mass parts

[table 1]

Constituent K	Amount (mass parts)
Constituent K	Amount (mass parts)	K pigment dispersing thing 1 (carbon black) propylene glycol monomethyl ether acetate MEK cementing agent 1 Hydroquinone monomethylether DPHA liquid polymerization initiator A surfactant 1	25 8.0 53 9.1 0.002 4.2 0.16 0.044

Preparation method to the resin combination K1 with light-proofness of record in the last table 1 describes below.

At first take by weighing the K pigment dispersing thing 1 of the amount of record in the table 1, propylene glycol monomethyl ether acetate, in temperature is under 24 ℃ (± 2 ℃), mixed 10 minutes with 150rpm, then take by weighing the cyclohexanone of the amount of record in the table 1 respectively, cementing agent-1, Hydroquinone monomethylether, DPHA liquid, polymerization initiator A (2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-diethoxy carbonyl methyl) amino-3 '-bromophenyl]-the s-triazine), surfactant 1, in temperature is under 25 ℃ (± 2 ℃), add successively according to said sequence, in temperature is under 40 ℃ (± 2 ℃), stirred 30 minutes with 150rpm, obtain having the resin combination K1 of light-proofness.

In addition, in the composition of in table 1, putting down in writing,

^*Consisting of of K pigment dispersing thing 1:

Carbon black (デグ Star サ society system, trade name: 13.1 mass parts Special Black250)

Above-mentioned pigment dispersing agent A (compound 7 shown in the general formula D 1) 0.65 mass parts

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand) 6.72 mass parts

Propylene glycol monomethyl ether acetate 79.53 mass parts

^*Consisting of of cementing agent-1:

Polymkeric substance be (methacrylic acid benzyl ester/methacrylic acid=78/22 mol ratio

Random copolymers, molecular weight 40,000) 27 mass parts

Propylene glycol monomethyl ether acetate 73 mass parts

^*Consisting of of DPHA liquid:

Dipentaerythritol acrylate (contain polymerization inhibitor MEHQ 500ppm,

Japan chemical drug (strain) society system, trade name KAYARAD DPHA) 76 mass parts

Propylene glycol monomethyl ether acetate 24 mass parts

In addition, this surfactant 1 is identical with the surfactant 1 that uses among the coating fluid H1 with above-mentioned thermoplastic resin.

[formation] with next door of light-proofness

For the alkali-free glass substrate, on one side spray the glass cleaner 20 seconds that is adjusted to 25 ℃ with perforated water spray, clean with rotating brush on one side with nylon hair, after using the pure water spray Cleaning for High Capacity again, spray silane coupling agent (0.3 quality % aqueous solution of N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan with perforated water spray, trade name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) society system) 20 seconds, and use the pure water spray Cleaning for High Capacity.This substrate was heated 2 minutes at 100 ℃ with the substrate preheating apparatus.

After the diaphragm of above-mentioned photosensitive resin transfer material K1 peeled off; with laminating machine (イ of Co., Ltd. Hitachi Application ダストリイズ system (LamicII type)), be set forth on 2 minutes the substrate of 100 ℃ of following heating last in the condition laminated that 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transporting velocity 2.2m/ divide.

After peeling off interim stilt, employing has the contiguous type exposure machine (the イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd. system) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this thermoplastic resin interlayer is 200 μ m, at 100mJ/cm ²Exposure under carry out pattern exposure.Mask shape is a clathrate, is being equivalent to the part of pixel with the boundary line in the next door with light-proofness, and the radius-of-curvature that makes the protrusion angle of next door one side with light-proofness is 0.6 μ m.

Then, (contain 30% triethanolamine with triethanolamine class developer solution, trade name: T-PD2, the description Off イ of Fuji Le system Co., Ltd. makes, with the liquid after the pure water dilution 12 times (mixing with the ratio of 11 parts of pure water) with 1 part of T-PD2) spray development by 30 ℃ of following 30 seconds, the condition of tack nozzle pressure 0.04MPa, remove thermoplastic resin and middle layer (oxygen barrier layers).

Then, (contain the sodium bicarbonate of 0.38 mol, the sodium carbonate of 0.47 mol, 5% nekal, anionic surfactant, defoamer, stabilizing agent with sodium carbonate class developer solution, trade name T-CD1, the description Off イ of Fuji Le system Co., Ltd. system, with the liquid after 5 times of the pure water dilutions), spray development by 29 ℃ of following 30 seconds, the condition of conical nozzle pressure 0.15MPa, resin bed with light-proofness is developed, obtain pattern portrayal next door (partition pattern) with light-proofness.

Then with clean-out system (trade name " T-SD3 (the description Off イ of Fuji Le system Co., Ltd. system) ", with the liquid after 10 times of the pure water dilutions), spray by 33 ℃ of following 20 seconds, the condition of conical nozzle pressure 0.02MPa, and remove residue with brush with nylon hair, obtain having the next door of light-proofness.Then, for this substrate, use extra-high-pressure mercury vapour lamp at 500mJ/cm from this resin bed one side again ²Illumination under carry out post-exposure, then 240 ℃ of following thermal treatments 50 minutes.

[plasma is refused water treatment]

Afterwards, carry out plasma with following method and refuse water treatment.

For the above-mentioned substrate that is formed with next door, use negative electrode manifold type parallel plate-type plasma processing apparatus to carry out plasma and refuse water treatment by following condition with light-proofness.

Using gases: CF ₄

Gas flow: 80sccm

Pressure: 40Pa

RF power: 50W

Processing time: 30sec

[preparation of ink-jet ink for color filter]

With reference to the special embodiment 1 that opens the 2002-201387 communique, by following formulation ink.

Table 2

Constituent content (mass parts)	R ink 1	R ink 2	R ink 3	R ink 4	R ink 5	R ink 6	R ink 7	G ink 1	B ink 1
Constituent content (mass parts)	R ink 1	R ink 2	R ink 3	R ink 4	R ink 5	R ink 6	R ink 7	G ink 1	B ink 1	Pigment dispensing composition A	51
Pigment dispensing composition B		51								Pigment dispensing composition A	51
Pigment dispensing composition B		51								Pigment dispensing composition C			51
Pigment dispensing composition D				51						Pigment dispensing composition C			51
Pigment dispensing composition D				51						Pigment dispensing composition E					51
Pigment dispensing composition F						51				Pigment dispensing composition E					51
Pigment dispensing composition F						51				Pigment dispensing composition G							51
G pigment (C.I.P.G.36)								6.0		Pigment dispensing composition G							51
G pigment (C.I.P.G.36)								6.0		B pigment (C.I.P.B.15:6)									6.0
Macromolecule dispersing agent (the ソ Le パ-ス 24000 of AVECIA corporate system)	2.2	2.2	2.2	2.2	2.2	2.2	2.2	2.0	2.0	B pigment (C.I.P.B.15:6)									6.0
	2.2	2.2	2.2	2.2	2.2	2.2	2.2	2.0	2.0	Cementing agent (methacrylic acid benzyl ester/methacrylic acid copolymer)								4.6	4.6
Olefin(e) acid ester in the dipentaerythritol five	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0									4.6	4.6
Olefin(e) acid ester in the dipentaerythritol five	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0	Tripropylene glycol diacrylate	4.5	4.5	4.5	4.5	4.5	4.5	4.5	5.0	5.0

2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane)-1-ketone	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0
	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0	2.0	Diethylene glycol single-butyl ether acetate, 29.9dyn/cm	44	44	44	44	44	44	44	80	80

About the mixing of each composition in the above-mentioned table 2, at first pigment and macromolecule dispersing agent are put in a part of solvent, mix, stir with 3 roller mixing rolls and bowl mill again, obtain dispersible pigment dispersion.On the other hand, other gradation composition is put in the remaining solvent, carried out stirring and dissolving and disperse, obtain binder solution.On one side dispersible pigment dispersion or pigment dispensing composition are added in the binder solution bit by bit, with dissolving machine fully stir preparation ink-jet ink for color filter on one side.

[pixel formation]

Use the piezoelectric type shower nozzle, R ink 1, G ink 1, the B ink 1 of above-mentioned acquisition is instilled into the recess that is surrounded by the light-proofness next door at first in the following manner.The result has just obtained color filter A of the present invention by following mode.

Shower nozzle has the density of 150 nozzles to have 318 nozzles by every 25.4mm, and it is fixed in 1/2 the nozzle mode at interval that staggers on two nozzle rows directions, instils 300 at the every 25.4mm of the orientation of substrate upper edge nozzle thus.

Shower nozzle and ink are controlled, and its mode is to carry out the warm water circulation in shower nozzle, thereby reaches 50 ± 0.5 ℃ near making the ejection part.

From shower nozzle ejection ink is to control by the piezoelectric drive signal that is applied to shower nozzle, can reach every ejection 6～42pl, in the present embodiment, on one side below shower nozzle 1mm place carry glass substrate, instil with shower nozzle in one side.Transporting velocity can be set at 50～200mm/s.In addition, Piezoelectric Driving frequency maximum can reach 4.6KHz, can control dropped amount by these settings.

Control transporting velocity, driving frequency, the amount of spreading that makes R, G, each pigment of B are 1.1,1.8,0.75g/m ², to R, G, the B corresponding recess of expection in instil R, G, B ink.

The ink that instils is transported to exposed portion, utilizes ultraviolet light-emitting diode (UV-LED) to expose.UV-LED uses day NCCU033 of inferior chemical society manufacturing.This LED is that output wavelength is the ultraviolet light of 365nm from the wafer, utilizes the electric current of about 500mA, can send the light of about 100mW from wafer.With a plurality of LED of being spaced of 7mm, can obtain 0.3W/cm from the teeth outwards ²Power.From the back of instiling to the time of exposing, and the time shutter can change in the distance of throughput direction according to the transporting velocity of medium and shower nozzle and LED.In the present embodiment, drip fall behind in 100 ℃ dry 10 minutes down, expose then.

Setting according to distance and transporting velocity can be adjusted to 0.01～15J/cm with the exposure energy on the medium ²Regulate exposure energy according to transporting velocity.

In the mensuration of these exposure powers, exposure energy, the spectroradiometer URS-40D that uses ウシオ motor to make adopts the integrated value between the wavelength 220nm to 400nm.

Glass substrate after instiling was toasted 30 minutes in 230 ℃ baking oven, thereby make light-proofness next door, each pixel full solidification simultaneously.

(formation of ITO electrode)

The glass substrate that has formed color filter is packed in the sputter equipment, behind the thick ITO (indium tin oxide) of 100 ℃ of comprehensive vacuum evaporation 1300 dusts, 240 ℃ down annealing made the ITO crystallization in 90 minutes, form ito transparent electrode, finished the making of color filter A.

Except the R1 ink that will use in making color filter A changes into R2～7, other is just the same with color filter A, making color filter B～G.

Measure the contrast of the red pixel of the above-mentioned color filter of the present invention that obtains with following method.The results are shown in Table 3.

[mensuration of contrast (ratio)]

As backlight assembly, use is provided with diffuser plate and the device that forms on cold-cathode tube light source (the LCD TV LC-22GD3 that uses SHARP society to make), between two polaroids (the polaroid POLAX-15N that (strain) Le ケオ society makes), place color filter, the Y value of the colourity of the light that polaroid is arranged on when being parallel to Nicol prism to be seen through is arranged at the Y value of the colourity of the light that is seen through when vertical with Nicol prism divided by polaroid, tries to achieve contrast.For the mensuration of colourity, use color briliancy instrument (BM-5A that (strain) トプコ Application society makes).

The position that is provided with about two polaroids, color filter, color briliancy instrument, the sample that polaroid directly is set in the back of backlight assembly and will measures, make through light and pass the polaroid that is arranged on the color briliancy instrument anterior locations, measure by being arranged at the locational color briliancy of 500mm instrument.The mensuration angle of color briliancy instrument is set at 2 °.Light quantity setting backlight becomes maximum.

Use small-sized cold-cathode tube light source, measure the zone that the TFCAM-7000 of system (trade name) measures about 60 μ m at back light unit with the micro-spectral of ラ system ダ PVC ジョ Application Co., Ltd. manufacturing, detect by light only, measure red pixel contrast alone the red pixel that sees through color filter.Adopt method same as described above to calculate contrast.

[photostability assay method]

With said determination the color filter of contrast be immersed in 10% the hydrofluoric acid solution after 1 minute, remove glass substrate, the TFCAM-7000 with ラ system ダ PVC ジョ Application Co., Ltd. makes measures the absorption spectrum that sees through of 100 R pixels at random, and averages.

Color filter after measuring is exposed with xenon light from this side with glass substrate, after the exposure, see through absorption spectrum with the same mensuration before the exposure,, obtain the survival rate of pigment by the ratio of the peak area that each pigment produced in the forward and backward resulting absorption spectrum of exposure.When the pigment more than 2 kinds share, calculate, carry out the waveform separation, thereby calculate the survival rate of single pigment according to known absorption spectrum.

The メリ one go one ラ Application De type fadeometer that adopts イ one グ Le エ Application ジニアリ Application グ society to make exposes, conditions of exposure for the xenon light that near infrared ray cut out by infrared ray absorbing wave filter (HA50) with 100,000 luxs, exposure 150 hours.

As shown in table 3, (contrast of A～C) is more than 5000 to color filter of the present invention, and the pigment survival rate has realized having concurrently simultaneously high-contrast and photostability after the xenon rayed in 60～95% scope.

Table 3

Pigment dispensing composition	The R ink-jet ink	Color filter	The contrast of color filter	Survival rate after the xenon rayed (%)
Pigment dispensing composition	The R ink-jet ink	Color filter	The contrast of color filter	Survival rate after the xenon rayed (%)	A	R ink 1	A	9800	85
B	R ink 2	B	14000	69	A	R ink 1	A	9800	85
B	R ink 2	B	14000	69	C	R ink 3	C	7500	91
D	R ink 4	D	3500	99	C	R ink 3	C	7500	91
D	R ink 4	D	3500	99	E	R ink 5	E	2600	97
F	R ink 6	F	5500	89	E	R ink 5	E	2600	97
F	R ink 6	F	5500	89	G	R ink 7	G	7000	48

(embodiment 2 comparative examples 2)

[making of liquid crystal indicator]

Make liquid crystal indicator and its display characteristic is estimated with the color filter of making in embodiment 1 comparative example 1.

(formation of dottle pin)

By with [embodiment 1] of TOHKEMY 2004-240335 communique in the identical method of dottle pin formation method of record, on the ito transparent electrode of above-mentioned making, form dottle pin.

(being used to control the formation of the projection of liquid crystal aligning)

Use following positive-working photosensitive resin layer coating fluid, on the above-mentioned ito transparent electrode that forms dottle pin, be formed for controlling the projection of liquid crystal aligning.

But exposure, development and roasting procedure adopt following method.

Proximity exposure machine (the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd. system) is installed, and making the photomask of regulation and the distance of photoresist laminar surface is 100 μ m, utilizes extra-high-pressure mercury vapour lamp with 150mJ/cm ²Irradiation energy see through this photomask and carry out proximity exposure.

Then, use 2.38% tetramethyl ammonium hydroxide aqueous solution, under 33 ℃, substrate was sprayed 30 seconds, develop by the fountain developing apparatus.Removed by development thus and do not needed part (exposed portion) on the photo-sensitive resin, thereby obtained the liquid crystal indicator substrate, wherein the color filter side at this substrate has formed the projection that is used to control liquid crystal aligning that is made of the photo-sensitive resin that forms desired pattern form.

Then, with the liquid crystal indicator that formed this projection that is used to control liquid crystal aligning with substrate 230 ℃ of bakings 30 minutes down, thereby form the projection that is used to control liquid crystal aligning of solidifying at liquid crystal indicator on substrate.

＜positive-working photosensitive resin layer is filled a prescription with coating fluid 〉

Positive corrosion-resisting agent liquid (FH-2413F that the Off イ of Fuji Le system エレ Network トロニ Network スマテリア Le ズ (strain) society makes) 53.3 mass parts

MEK 46.7 mass parts

0.04 part of メガ Off ア Star Network F-780F (big Japanese ink chemical industry (strain) society system)

(making of liquid crystal indicator)

The alignment films that is made of polyimide is set at the liquid crystal indicator of above-mentioned acquisition on substrate again.

Then, the position that is equivalent to housing of the black matrix around being arranged at, printing epoxy encapsulant in the mode of surrounding the color filter pixel group, the MVA pattern that instils simultaneously liquid crystal, and paste with relative substrate, then the substrate of pasting is heat-treated, make sealant cures.On the two sides of the liquid crystal cell that obtains by this way, paste the polaroid HLC2-2518 that (strain) サ Application リ Star society makes.Then, backlight by three-wavelength cold-cathode tube light source (the FWL 18EX-N that the ライ of Toshiba Star Network (strain) society makes) structure, it is installed in the rear side of the liquid crystal cell that is provided with above-mentioned polaroid, form liquid crystal indicator A.

Except changing into respectively color filter B～G by used color filter A when making liquid crystal indicator A, other is just the same with liquid crystal indicator A, making liquid crystal indicator B～G.

The evaluation of＜liquid crystal indicator 〉

-1. the evaluation of burning screen fault

Formed each liquid crystal indicator, computing method according to the minimum best common voltage of the described flicker of Fig. 4 B (flicker) of TOHKEMY 2000-275645 communique, be determined at the remnant DC voltages that produces in the liquid crystal cell, as the index of burning the screen fault.

In addition, the remnant DC voltages of mensuration is more little, show more can inhibition of sintering screen fault generation.At this, remnant DC voltages is designated as " produce and burn the screen phenomenon " when being designated as " produce a little and burn the screen phenomenon ", remnant DC voltages more than or equal to 100mV when being designated as " do not produce and burn the screen phenomenon ", remnant DC voltages less than 100mV during less than 80mV.The result is as shown in table 4.

-2. the evaluation of display characteristic

10 people groups (パネラ once) to display characteristic (1) black density, (2) redness of each liquid crystal indicator of made describe power, (3) are monochromatic whether red inhomogeneous the evaluation is arranged when showing.In the evaluation in following each stage, 10 personal evaluations' mean value is as shown in table 4.

Liquid crystal indicator A～C of the present invention has photostability and high-contrast simultaneously, and display characteristic also is improved when being used for display panel, compares with Comparative Example D～G, and they have the overall performance of inundatory excellence as can be seen.

(1) black density

5: the black density is good.

4: black density no problem (good).

3: black is felt burnt hair (common) a little a little.

2: the black look burnt hair (poor slightly) that gets up.

1: black reproduces poor (non-constant).

(2) redness is described power

5: redness is described the power excellence

4: redness is described power no problem (very)

3: redness is described power not enough (common) a little

2: redness is described power deficiency (poor slightly)

1: red reproduction poor (non-constant)

(3) red inhomogeneous

5: can't see red inhomogeneous at all

4: do not have red uneven problem (very)

3: feel red inhomogeneous (common) a little

2: be clear that red inhomogeneous (poor slightly)

1: see red inhomogeneous (non-constant) significantly

Table 4

Pigment dispensing composition	Ink-jet ink	Liquid crystal indicator	Burn screen	The black density	Redness is described power	Red inhomogeneous
Pigment dispensing composition	Ink-jet ink	Liquid crystal indicator	Burn screen	The black density	Redness is described power	Red inhomogeneous	A	R ink 1	A	Do not have	4.8	5.0	5.0
B	R ink 2	B	Do not have	5.0	4.8	4.7	A	R ink 1	A	Do not have	4.8	5.0	5.0
B	R ink 2	B	Do not have	5.0	4.8	4.7	C	R ink 3	C	Do not have	4.6	4.8	5.0
D	R ink 4	D	Do not have	3.2	2.2	4.4	C	R ink 3	C	Do not have	4.6	4.8	5.0
D	R ink 4	D	Do not have	3.2	2.2	4.4	E	R ink 5	E	Do not have	2.7	1.9	3.2
F	R ink 6	F	Have slightly	3.1	2.5	1.9	E	R ink 5	E	Do not have	2.7	1.9	3.2
F	R ink 6	F	Have slightly	3.1	2.5	1.9	G	R ink 7	G	Have	4.5	3.5	2.1

(embodiment 3 comparative examples 3)

Above-mentioned pigment dispensing composition A is mixed with other composition, constitute the composition of following table 5-1, preparation color filter photosensitive composition A.

[table 5-1]

Constituent	Amount (mass parts)
Constituent	Amount (mass parts)	Pigment dispensing composition A propylene glycol monomethyl ether acetate MEK cementing agent 11 DPHA liquid 2-, three chloro-5-(right-the styryl styryl)-1,3,4-oxadiazole polymerization initiator A phenothiazine surfactant 2	44.5 7.6 37 0.7 3.8 0.12 0.05 0.01 0.06

＜cementing agent-11 〉

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

Propylene glycol monomethyl ether acetate 73 mass parts

＜DPHA liquid 〉

Dipentaerythritol acrylate (containing polymerization inhibitor MEHQ 500ppm, Japanese chemical drug (strain) society system, trade name KAYARAD DPHA) 76 mass parts

Propylene glycol monomethyl ether acetate 24 mass parts

＜surfactant 2 〉

Following compound 1 30 mass parts

MEK 70 mass parts

Compound 1

(n=6, x=5 5, y=5, Mw=33940, Mw/Mn=2.55, PO: epoxypropane, EO: oxirane)

With pigment dispensing composition B～G replacement pigment dispensing composition A, all the other prepare color filter photosensitive composition B～G respectively with above-mentioned the same except respectively.

[making of color filter (making)] by using the slit-shaped nozzle to apply

[formation of black (K) image]

After with the UV cleaning device alkali-free glass substrate being cleaned, clean with brush with clean-out system, again with the ultrapure water ultrasonic cleaning.120 ℃ of following thermal treatments 3 minutes, make surface state stable this substrate.

Cool off this substrate, regulate its temperature to 23 ℃, (エ Off エ one エスアジア Co., Ltd. makes with coating machine with the glass substrate that has the slit-shaped nozzle, trade name: MH-1600), except with surfactant 2 substitution list surface-active agents 1, with the cementing agent 2 replacement cementing agents 1, will apply by the photosensitive composition K1 that constituent constituted of record in the last table 1.Next, with VCD (Minton dryer; Tokyo Applied Chemistry Industrial Co., Ltd. makes) dry 30 seconds, make the part of solvent dry, after the no flowability of layer to be applied,, obtain the photo-sensitive resin K1 of thickness 2.4 μ m 120 ℃ of following prebake 3 minutes.

At first take by weighing K pigment dispersing thing 1, propylene glycol monomethyl ether acetate, be under 24 ℃ (± 2 ℃) in temperature, mix stirring 10 minutes with 150rpm, then take by weighing MEK, cementing agent-2, Hydroquinone monomethylether, DPHA liquid, polymerization initiator A, surfactant 1 respectively, in temperature is under 25 ℃ (± 2 ℃), add successively according to said sequence, in temperature is under 40 ℃ (± 2 ℃), stirs 30 minutes with 150rpm, obtains described photosensitive composition K1.

＜K pigment dispersing thing 1 〉

Carbon black (trade name: Nipex 35, デグサジャパ Application society system) 13.1 mass parts

Spreading agent (following compound 2J) 0.65 mass parts

Polymkeric substance be (methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio

Random copolymers, molecular weight 3.7 ten thousand) 6.72 mass parts

Propylene glycol monomethyl ether acetate 79.53 mass parts

＜cementing agent-2 〉

Random copolymers, molecular weight 3.8 ten thousand) 27 mass parts

Propylene glycol monomethyl ether acetate 73 mass parts

Employing has the contiguous type exposure machine (the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd. system) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this photoresist interlayer is 200 μ m, at 300mJ/cm ²Exposure under carry out pattern exposure.

Next, with spray spout pure water is sprayed, after making the surface of this photo-sensitive resin K1 evenly wetting, (contain KOH, non-ionic surfactant with KOH class developer solution, trade name: CDK-1, the Off イ of Fuji Le system エレ Network トロニ Network スマテア Le ズ company makes, the liquid after dilute 100 times) be spray development 80 seconds under the 0.04MPa at 23 ℃, the pressure of tack nozzle, obtain having the image of pattern.Next, under the pressure of 9.8MPa, spray ultrapure water, remove residue, deceived the image of (K) with the UHV (ultra-high voltage) washer jet.Then 220 ℃ of following thermal treatments 30 minutes.

[formation of red (R) pixel]

On the substrate that is formed with above-mentioned image K, use above-mentioned photosensitive composition A, according to form the above-mentioned black identical operation of (K) image, after thermal treatment is finished, form pixel R.The film thickness of this photo-sensitive resin R1 and the coating amount of pigment are as follows.In addition, the preparation of photosensitive composition A order is the same with photosensitive composition K1.

Photoresist film thickness (μ m) 1.60

Pigment coating amount (g/m ²) 1.00

C.I.P.R.254 coating amount (g/m ²) 0.80

[formation of green (G) pixel]

On the substrate that is formed with above-mentioned image K and pixel R, use by the photosensitive composition G1 that constituent constituted that puts down in writing among the following table 5-4, according to form the above-mentioned black identical operation of (K) image, after thermal treatment is finished, form pixel G.The film thickness of this photo-sensitive resin G1 and the coating amount of pigment are as follows.In addition, the preparation of photosensitive composition G1 order is the same with photosensitive composition K1.

Photoresist film thickness (μ m) 1.60

Pigment coating amount (g/m ²) 1.92

C.I.P.G.36 coating amount (g/m ²) 1.34

C.I.P.Y.150 coating amount (g/m ²) 0.58

[table 5-4]

Constituent	Amount (mass parts)
Constituent	Amount (mass parts)	G pigment dispersing thing 1 (CIPG 36) Y pigment dispersing thing 1 (CIPY 150) propylene glycol monomethyl ether acetate MEK cyclohexanone cementing agent 2 DPHA liquid 2-, three chloro-5-(right-the styryl styryl)-1,3,4-oxadiazole polymerization initiator A phenothiazine surfactant 2	28 15 29 26 1.3 2.5 3.5 0.12 0.05 0.01 0.07

＜G pigment dispersing thing 1 〉

The Off イ of Fuji Le system エレ Network トロニ Network スマテア Le ズ Co., Ltd. makes (trade name: GT-2)

＜Y pigment dispersing thing 1 〉

Mikoku Pigment Co., Ltd. makes (the yellow EX3393 of trade name: CF)

[formation of blue (B) pixel]

On the substrate that is formed with above-mentioned image K, pixel R and pixel G, use is by the photosensitive composition B1 that constituent constituted that puts down in writing among the following table 5-5, according to form the above-mentioned black identical operation of (K) image, after thermal treatment is finished, form pixel B, obtain target color filter AA.The film thickness of this photo-sensitive resin B1 and the coating amount of pigment are as follows.In addition, the preparation of photosensitive composition G1 order is the same with photosensitive composition K1.

Photoresist film thickness (μ m) 1.60

Pigment coating amount (g/m ²) 0.75

C.I.P.B.15:6 coating amount (g/m ²) 0.705

C.I.P.V.23 coating amount (g/m ²) 0.045

[table 5-5]

Constituent	Amount (mass parts)
Constituent	Amount (mass parts)	B pigment dispersing thing 1 (CIPB 15:6) B pigment dispersing thing 2 (CIPB 15:6+CIP V23) propylene glycol monomethyl ether acetate MEK cementing agent 3 DPHA liquid 2-, three chloro-5-(right-the styryl styryl)-1,3,4-oxadiazole phenothiazine surfactant 2	8.6 15.0 28 26 17.2 4.0 0.17 0.02 0.06

＜B pigment dispersing thing 1 〉

Mikoku Pigment Co., Ltd. makes (the blue EX3357 of trade name: CF)

＜B pigment dispersing thing 2 〉

Mikoku Pigment Co., Ltd. makes (the blue EX3383 of trade name: CF)

＜cementing agent-3 〉

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, molecular weight 3.8 ten thousand) 27 mass parts

Propylene glycol monomethyl ether acetate 73 mass parts

For the method for making of color filter AA, except replacing the photosensitive composition A with photosensitive composition B～G, other is the same with the method for making color filter AA, makes color filter AB～AG.

The same with embodiment 1 comparative example 1, measure the contrast and the photostability of each color filter respectively.The result shows, color filter of the present invention (contrast of AA～AC) be more than 5000, after the xenon rayed pigment survival rate in 60～95% scope, (AD～AG) compare, (AA～AC) has high-contrast and photostability to color filter of the present invention simultaneously with the color filter of comparative example.

(embodiment 4 comparative examples 4)

[making of liquid crystal indicator and evaluation]

Make liquid crystal indicator and estimate its display characteristic with color filter AA～AG.

(formation of ITO electrode)

The substrate that has formed color filter is packed in the sputter equipment, behind the thick ITO (indium tin oxide) of 100 ℃ of comprehensive vacuum evaporation 1300 dusts, 240 ℃ down annealing made the ITO crystallization in 90 minutes, form ito transparent electrode.

(formation of dottle pin)

But exposure, development and roasting procedure adopt following method.

Then, use 2.38% tetramethyl ammonium hydroxide aqueous solution, under 33 ℃, sprayed 30 seconds, develop to substrate by the fountain developing apparatus.Removed by development thus and do not needed part (exposed portion) on the photo-sensitive resin, thereby obtained the liquid crystal indicator substrate, wherein the color filter side at this substrate has formed the projection that is used to control liquid crystal aligning that is made of the photo-sensitive resin that forms desired pattern form.

Positive corrosion-resisting agent liquid (the Off イ of Fuji Le system エレ Network トロニ Network スマ

The FH-241 3F that テリア Le ズ (strain) society makes) 53.3 mass parts

MEK 46.7 mass parts

(making of liquid crystal indicator)

Then, the position that is equivalent to housing of the black matrix around being arranged at, printing epoxy encapsulant in the mode of surrounding the color filter pixel group, the MVA pattern that instils simultaneously liquid crystal, and paste with relative substrate, then the substrate of pasting is heat-treated, make sealant cures.On the two sides of the liquid crystal cell that obtains by this way, paste the polaroid HLC2-2518 that (strain) サ Application リ Star society makes.Then, backlight by three-wavelength cold-cathode tube light source (FWL18EX-N that the ライ of Toshiba Star Network (strain) society makes) structure, it is installed in the rear side of the liquid crystal cell that is provided with above-mentioned polaroid, form liquid crystal indicator.

The same with embodiment 2 comparative examples 2, measure the display characteristic of each liquid crystal indicator AA～AG respectively.The result shows, compare with the liquid crystal indicator of the color filter AD～AG that uses comparative example, use the liquid crystal indicator of color filter AA～AC of the present invention to show good display characteristic, wherein black density and redness are described the equal excellence of power, are not shown uneven phenomenon.

(embodiment 5 comparative examples 5)

The making of＜color filter (making)〉by the laminated photosensitive resin transfer material

The same with embodiment 1 comparative example 1, preparation photosensitive resin transfer material K1 forms black (K) image.

Next, following photosensitive composition R101, G101 and B101 that constituent constituted that preparation is put down in writing by following table 5-6～5-8, and make each color pixel.

[table 5-6]＜photosensitive composition R101 〉

Constituent	Amount (mass parts)
Constituent	Amount (mass parts)	Pigment dispersing thing A R pigment dispersing thing 2 (CIPR 177) propylene glycol monomethyl ether acetate MEK	40 4.5 7.6 37

Cementing agent 1 DPHA liquid 2-three chloro-5-(right-the styryl styryl)-1,3,4-oxadiazole polymerization initiator A phenothiazine adjuvant 1 surfactant 2

0.8 4.4 0.14 0.06 0.01 0.52 0.06

[table 5-7]＜photosensitive composition G101 〉

Constituent	Amount (mass parts)
Constituent	Amount (mass parts)	G pigment dispersing thing 1 (CIPG36) Y pigment dispersing thing 1 (CIPY 150) propylene glycol monomethyl ether acetate MEK cyclohexanone cementing agent 2 DPHA liquid 2-, three chloro-5-(right-the styryl styryl)-1,3,4-oxadiazole polymerization initiator A phenothiazine surfactant 2	28 15 29 26 1.3 3.0 4.3 0.15 0.06 0.01 0.07

[table 5-8]＜photosensitive composition B101 〉

Constituent	Amount (mass parts)
Constituent	Amount (mass parts)	B pigment dispersing thing 1 (CIPB 15:6) B pigment dispersing thing 2 (CIPB 15:6+CIPV23) propylene glycol monomethyl ether acetate MEK cementing agent 3 DPHA liquid 2-, three chloro-5-(right-the styryl styryl)-1,3,4-oxadiazole phenothiazine surfactant 2	8.6 15.0 28 26 18.5 4.3 0.17 0.02 0.06

＜adjuvant 1 〉

The agent of phosphoric acid ester sp act

(nanmu changes into Co., Ltd. and makes, trade name: HIPLAAD ED 152).

[formation of red (R) pixel]

Use above-mentioned photosensitive resin transfer material R101,, obtain red (R) the pixel R after the thermal treatment according to the operation identical with the operation of above-mentioned photosensitive resin transfer material K1.But exposure is 40mJ/cm ², the condition during with sodium carbonate class developing liquid developing is 35 ℃, 35 seconds.The coating amount of the film thickness of this photo-sensitive resin R101 and pigment (C.I.P.R.254 and C.I.P.R.177) is as follows.

Photoresist film thickness (μ m) 2.00

Pigment coating amount (g/m ²) 1.00

C.I.P.R.254 coating amount (g/m ²) 0.80

C.I.P.R.177 coating amount (g/m ²) 0.20

The substrate that will be formed with above-mentioned image K and pixel R cleans, and with after the pure water spray Cleaning for High Capacity, does not use silane coupling solution with brush again, delivers in the substrate preheating device.

[formation of green (G) pixel]

Use above-mentioned photosensitive resin transfer material G101,, obtain green (G) the pixel G after the thermal treatment according to the operation identical with the operation of above-mentioned photosensitive resin transfer material R101.But exposure is 40mJ/cm ², the condition during with sodium carbonate class developing liquid developing is 34 ℃, 45 seconds.The coating amount of the film thickness of this photo-sensitive resin G101 and pigment (C.I.P.G.36 and C.I.P.Y.150) is as follows.

Photoresist film thickness (μ m) 2.00

Pigment coating amount (g/m ²) 1.92

C.I.P.G.36 coating amount (g/m ²) 1.34

C.I.P.Y.150 coating amount (g/m ²) 0.58

The substrate that will be formed with above-mentioned image K, pixel R and pixel G cleans, and with after the pure water spray Cleaning for High Capacity, does not use silane coupling solution with brush again, delivers in the substrate preheating device.

[formation of blue (B) pixel]

Use above-mentioned photosensitive resin transfer material B101,, obtain indigo plant (B) pixel B after the thermal treatment according to the operation identical with the operation of above-mentioned photosensitive resin transfer material R101.But exposure is 30mJ/cm ², the condition during with sodium carbonate class developing liquid developing is 36 ℃ of C, 40 seconds.The coating amount of the film thickness of this photo-sensitive resin B101 and pigment (C.I.P.B.15:6 and C.I.P.V.23) is as follows.

Photoresist film thickness (μ m) 2.00

Pigment coating amount (g/m ²) 0.75

C.I.P.B.15:6 coating amount (g/m ²) 0.705

C.I.P.V.23 coating amount (g/m ²) 0.045

The substrate that will be formed with above-mentioned pixel R, pixel G, pixel B and image K cured under 240 ℃ 50 minutes, obtained color filter A1.

For the method for making of above-mentioned color filter A1, pigment dispensing composition A is replaced by pigment dispensing composition B～G respectively, make color filter B1～G1.

The same with embodiment 3 comparative examples 3, measure contrast and the photostability of resulting color filter A1～G1.The result shows, the contrast of color filter of the present invention be the survival rate of pigment more than 5000, after the xenon rayed in 60～95% scope, contrast is high, photostability is excellent.

(embodiment 6 comparative examples 6)

[making of liquid crystal indicator and evaluation]

According to the same method of embodiment 2 comparative examples 2, use color filter A1～G1 to make liquid crystal indicator, and estimate its display characteristic.

The result shows, compare with the liquid crystal indicator of the color filter D1～G1 that uses comparative example, use the liquid crystal indicator of color filter A1～C1 of the present invention to show good display characteristic, wherein black density and redness are described the equal excellence of power, are not shown uneven phenomenon.

(embodiment 7 comparative examples 7)

(comparative example)

[making of CCD device]

(the CCD making of dispersible pigment dispersion)

According to following prescription, use above-mentioned pigment dispensing composition F, make dispersible pigment dispersion (1) ... green G, (2) ... blue B, (3) ... red R.

Dispersible pigment dispersion (1)

C.I.P.G.36 95 mass parts

C.I.P.G.7 30 mass parts

C.I.P.Y.139 45 mass parts

PLAAD ED151 20 mass parts

(nanmu originally changes into (strain) system)

Methacrylic acid benzyl ester/methacrylic acid copolymer 25 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 625 mass parts

Dispersible pigment dispersion (2)

C.I.P.B.15:6 125 mass parts

C.I.P.V.23 20 mass parts

PLAAD ED151 40 mass parts

(nanmu originally changes into (strain) system)

Methacrylic acid benzyl ester/methacrylic acid copolymer 25 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 790 mass parts

Dispersible pigment dispersion (3)

Pigment dispensing composition F 600 mass parts

Dispersing agent C of the present invention-16 40 mass parts

Methacrylic acid benzyl ester/methacrylic acid copolymer 25 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 345 mass parts

(preparation of colored resin composition)

Each 200 mass parts of versicolor dispersible pigment dispersion for above-mentioned acquisition mix with stirring machine and following composition respectively, and preparation is used for versicolor color filter colored resin composition.

＜form

Methacrylic acid benzyl ester/methacrylic acid copolymer 35 mass parts (copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Dipentaerythritol five acrylate 38 mass parts

Propylene glycol monomethyl ether acetate 120 mass parts

3-ethoxyl ethyl propionate 40 mass parts

Halomethyl triazines initiating agent 4 mass parts

(Photoepolymerizationinitiater initiater, goods name: TAZ107 body どり chemistry (strain) system)

(making of color filter and CCD device)

Mix following composition with stirring machine, preparation planarization film resist liquid.

＜form

Methacrylic acid benzyl ester/methacrylic acid copolymer 165 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Dipentaerythritol five acrylate 65 mass parts

Propylene glycol monomethyl ether acetate 138 mass parts

3-ethoxyl ethyl propionate 123 mass parts

Halomethyl triazines initiating agent 3 mass parts

The planarization that obtains is uniformly coated on the 6-inch silicon chip that has formed photodiode with the rotary coating machine with resist liquid.In addition, regulate the revolution of rotary coating machine, making the thickness of coating back after heat-treating with electric furnace under 100 ℃ * 120 seconds conditions of coated film surface temperature is about 1.5 μ m.

Then, be positioned over 220 ℃ baking oven 1 hour, coated film is solidified, form planarization film according to the mode that the photodiode surface that forms on the silicon chip is covered equally.

Then, for shades of colour, order according to G, R, B, coating is the above-mentioned color filter colored resin composition of 100 mass parts with respect to above-mentioned planarization film with resist liquid preparation prescription on above-mentioned planarization film, and carry out that drying (prebake conditions), pattern exposure, alkali are developed, flushing, solidify dry (back baking), form the pigmentary resin tunicle, thereby made color filter having on the silicon chip of photodiode.

In addition, pattern exposure is the mask pattern by 2 μ m, uses i line stepping exposure machine (trade name: FPA-3000i5+, キヤノ Application (strain) system) at 500mJ/cm ²Condition under carry out.

In addition, alkali develops and is to use organic basic developer solution (trade name: CD-2000, the Off イ of Fuji Le system エレ Network トロニ Network スマテリア Le ズ (strain) system) 40 quality % aqueous solution, the stirring of at room temperature carrying out 60 seconds is developed, utilize revolving distributor to carry out 20 seconds pure water rinsing then, clean with pure water again.Afterwards, blow down water droplet, make the substrate air dry, obtain pattern, on electric furnace, implement the back baking then and handle with 200 ℃ of conditions of 5 minutes of surface temperature with high temperature air.

On digital camera, install by the CCD device that obtains with upper type, under same light source, the colour chart that has KODAK system gray scale photographed, on monitor during observable image, observe image rock and red inhomogeneous.

Replace above-mentioned pigment dispensing composition F with pigment dispensing composition A, in addition, by making the CCD device, this CCD device is installed on digital camera with comparative example 3 identical modes, when carrying out same evaluation, obtained rocking less and having the image of even smooth color.In addition, when changing pigment dispensing composition B, C into, can confirm to have obtained equally to rock few image.

Claims

1. color filter, it is characterized in that, this color filter is formed by the dispersion thing of organic pigment particulate, in air, be that the survival rate of xenon rayed described pigment after 150 hours of 100,000 luxs is 60～95% with illuminance, and this color filter has contrast for more than or equal to 5000 pixel before the xenon rayed.

2. the described color filter of claim 1 is characterized in that, described organic pigment particulate is made of red pigment.

3. claim 1 or 2 described color filters is characterized in that, the survival rate of described pigment is 75～90%.

4. any described color filter in the claim 1～3 is characterized in that the contrast before described xenon rayed is more than or equal to 10000.

5. any described color filter in the claim 1～4 is characterized in that the contrast of the red pixel of color filter is more than or equal to 10000 before described xenon rayed.

6. a liquid crystal indicator is characterized in that, has any described color filter in the claim 1～5.

7. the described liquid crystal indicator of claim 6 is characterized in that, described liquid crystal indicator is the VA mode.

8. a CCD device is characterized in that, has any described color filter in the claim 1～5.