CN102193312B - Curing composition, color filter and manufacturing method thereof, liquid crystal display and image display apparatus - Google Patents

Abstract

The invention is implemented on the basis of the situation in the past, the purpose of which is to provide a curing composition for blue or magenta that can form colour pixels that can display good brightness.hue and are excellent in chemical resistance and can undergo thermosetting process. The curing composition comprises a dipyrromethene series dye, a polymerized monomer, an organic solvent, and a hydrogen providing compound, the hydrogen providing compound having at least two speculated function groups and being solid at 25 DEG C under a pressure of 1 atm. The invention further provides a colour filter and a method for manufacturing the same, a liquid crystal display, and an image display apparatus.

Description

Solidification compound, color filter and manufacture method thereof, liquid crystal display, image display

Technical field

The present invention relates to solidification compound, color filter and manufacture method thereof, liquid crystal display, image display.

Background technology

In recent years, along with personal computer, the particularly development of large picture LCD TV, there is the tendency of the increase in demand of liquid crystal display (LCD), especially colour liquid crystal display device.Usually, in colour liquid crystal display device, use the color filter of the colored pattern that possesses redness (R), green (G) and blue (B) this 3 primary colors always.In possessing the liquid crystal display of this color filter, the electrode corresponding with R, G and B pixel separately by open and close, thus liquid crystal is worked as shutter (shutter), light carries out colour by R, G and B pixel separately and shows.

Carried out various research about color filter, for example, in patent documentation 1, disclose and adopted the cured composition for color that contains two pyrroles's methylene base system metal complex compounds to manufacture color filter by colored resist (color resist) method.

About the printing ink of blueness of record in patent documentation 1, with the printing ink of other colors, compare, required having relatively high expectations in practicality, resulting colored pixels must show the thermotolerance of good form and aspect, brightness and excellence and chemical proofing etc.

Patent documentation

Patent documentation 1: TOHKEMY 2008-292970 communique

Summary of the invention

In recent years, about the thermotolerance of color filter, from be applied to the aspects such as manufacturing process of implementing under hot conditions more, it requires level to become very high.

On the other hand, the present inventors find, while using in patent documentation 1 concrete disclosed solidification compound, the form and aspect of resulting colored pixels recently require under stable on heating high temperature level easily deteriorated, not necessarily satisfactory in practicality.

In addition, in recent years, the raising that requires level of the optical characteristics such as tone of relevant display is also very remarkable, in order to tackle it, needs further to improve the brightness form and aspect of the colored pixels in color filter.On the other hand, use concrete disclosed solidification compound in patent documentation 1 to utilize the heat curing processing to carry out curing research, the absorption spectrum of colored pixels broadens as a result, can't obtain showing desired form and aspect and the colored pixels of brightness.

The present invention In view of the foregoing carries out, the solidification compound that provides a kind of blueness or magenta to use is provided its purpose, it can form and show good brightness form and aspect and the colored pixels of thermotolerance and chemical proofing excellence, can tackle heat curing process.

And then, the color filter of the excellents such as a kind of optical characteristics obtained by this solidification compound, thermotolerance, chemical proofing and the manufacture method with color filter of this specific character are provided.

The present inventors conduct in-depth research, and found that, have particular functional group's giving property of hydrogen compound by use, can manufacture the excellent colored pixels such as brightness, form and aspect, thermotolerance, chemical proofing.

That is, the present inventors find, above-mentioned problem can be by following<1 >～<11 formation solve.

<1 > a kind of solidification compound, its contain choosing freely the dyestuff shown in general formula described later (1-1), the dyestuff shown in general formula (1-2), and general formula (1-3) shown in the group that forms of dyestuff at least a kind of dyestuff, polymerizable monomer, organic solvent and giving property of hydrogen compound, described giving property of hydrogen compound at least has 2 functional groups in the group of selecting free hydroxyl, carboxyl, amide group, sulfonic group and phosphonate group to form, under 25 ℃, 1 atmospheric pressure, it is solid, and molecular weight is that (in addition, 2 carboxyls also can bondings and formed anhydride group below 3000.In addition, carboxyl and amide group also can bondings and are formed imide.)，

The content of above-mentioned giving property of hydrogen compound is 0.1～12 quality %.

<2>according to<1>described solidification compound, wherein, the quality (W of above-mentioned giving property of hydrogen compound ₁) with the quality (W of above-mentioned dyestuff ₂) mass ratio (W ₂/ W ₁) be 0.05～10.

<3 > according to<1 > or<2 > described solidification compound, wherein, the molecular weight of above-mentioned giving property of hydrogen compound is more than 36 with the ratio (molecular weight/functional group's number) of above-mentioned functional group number.

<4 > according to<1 >～<3 > the middle described solidification compound of any one, its viscosity under 25 ℃ is below 30mPas.

<5 > according to<1 >～<4 > the middle described solidification compound of any one, its surface tension under 25 ℃ is 20～40mN/m.

<6 > according to<1 >～<5 > the middle described solidification compound of any one, it also contains the dyestuff shown in general formula described later (3).

<7 > a kind of manufacture method of color filter, it possesses following operation: describe operation, the recess of dividing for the next door by being formed on substrate, by ink-jet method give<1～<6 in the described solidification compound of any one; With

Curing process, heated the above-mentioned solidification compound that is ejected into recess.

<8 > a kind of manufacture method of color filter, it has following operation: the recess divided in the next door by being formed on substrate coating<1 >～<6 in the described solidification compound of any one, Jie carries out pattern exposure by mask, and is developed, thereby forms pattern image.

<9 > a kind of color filter, it is by<7 > or<8 > described color filter manufacture method manufacture obtains.

<10 > a kind of liquid crystal display, it possesses<and 9 > described color filter.

<11 > a kind of image display, it possesses<and 9 > described color filter.

According to the present invention, the solidification compound that can provide a kind of blueness or magenta to use, it can form and show good brightness form and aspect and the colored pixels of thermotolerance and chemical proofing excellence, can tackle heat curing process.

And then, the color filter of the excellents such as a kind of optical characteristics obtained by this solidification compound, thermotolerance, chemical proofing and the manufacture method with color filter of this specific character also are provided.

The accompanying drawing explanation

Fig. 1 means the process flow diagram of the manufacturing process in the embodiment of manufacture method of color filter of the present invention.

Fig. 2 (a)～(f) is respectively according to the substrate shown in the order of the manufacturing process from substrate to color filter in the manufacture method of color filter of the present invention and the schematic section of color filter.

Reference numeral

10 color filters

12 substrates

14 next doors

16 recesses

18 printing ink

The uncured pixel printing ink of 18a

20 pixels

22 diaphragms

Embodiment

Below, to solidification compound of the present invention, use this solidification compound and the color filter and the manufacture method thereof that obtain are elaborated.

<solidification compound >

At first, solidification compound of the present invention is elaborated.

Solidification compound of the present invention contain choosing freely the dyestuff shown in general formula described later (1-1), the dyestuff shown in general formula (1-2), and general formula (1-3) shown in the group that forms of dyestuff at least a kind of dyestuff, polymerizable monomer, organic solvent and giving property of hydrogen compound, the functional group that described giving property of hydrogen compound at least has 2 regulations, and be solid under 25 ℃, 1 atmospheric pressure.

The present inventors find, can't obtain showing that the reason of colored pixels of desired form and aspect and brightness is relevant with the dyestuff cohesion each other in colored pixels, as its solution, have expected giving property of the hydrogen compound that use has specified functional groups.

That is,, in the present invention, there are giving property of the hydrogen compound of functional group of giving property of hydrogen of regulation and two pyrroles's methylene based dyes shown in general formula (1-1)～general formula (1-3) and interact, thereby performance suppresses the effect of dyestuff cohesion each other.Consequently, can suppress to make solidification compound to solidify and dyestuff cohesion each other in the colored pixels that obtains.And then, can obtain the colored pixels that optical characteristics such as showing desired form and aspect and brightness and thermotolerance, chemical proofing also are improved.

Below, each constituent (dyestuff, polymerizable monomer, organic solvent, giving property of hydrogen compound etc.) of solidification compound is described in detail.

Dyestuff shown in<general formula (1-1)～general formula (1-3) >

Solidification compound of the present invention contain at least a kind select the dyestuff shown in the dyestuff shown in free general formula (1-1), general formula (1-2), and general formula (1-3) shown in the group that forms of dyestuff in two pyrroles's methylene based dyes.

By using this two pyrroles methylene based dye, can form blueness with excellent form and aspect and brightness or the colored pixels of magenta.Wherein, if use the dyestuff shown in general formula described later (1-2), can form the more excellent colored pixels of form and aspect brightness thermotolerance chemical proofing.In addition, these dyestuffs can only be used a kind, and also two or more kinds may be used.

Below the dyestuff shown in various is described in detail.

Dyestuff shown in<general formula (1-1) >

Below, each substituting group of the dyestuff shown in mutual-through type (1-1) is described in detail.

General formula (1-1)

In general formula (1-1), R ₁₁～R ₁₆mean independently respectively hydrogen atom or substituting group.As R ₁₁～R ₁₆in substituting group, for example can list halogen atom (fluorine atom for example, the chlorine atom, bromine atoms, the iodine atom), (preferably carbon number is 1～48 to alkyl, the straight chain that more preferably carbon number is 1～24, the alkyl of side chain or ring-type, for example methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, the 2-ethylhexyl, dodecyl, cetyl, cyclopropyl, cyclopentyl, cyclohexyl, the 1-norborny, the 1-adamantyl), (preferably carbon number is 2～48 to alkenyl, the alkenyl that more preferably carbon number is 2～18, for example vinyl, allyl, 3-butene-1-yl), (preferably carbon number is 6～48 to aryl, the aryl that more preferably carbon number is 6～24, for example phenyl, naphthyl), (preferably carbon number is 1～32 to heterocyclic radical, the heterocyclic radical that more preferably carbon number is 1～18, for example thiphene ring, pyridine ring, furan nucleus, pyrimidine ring, the benzotriazole ring, pyrazole ring, imidazole ring, thiazole ring, the isothiazole ring, oxazole ring, Thiadiazole, triazole ring, the benzothiazole ring, benzoxazole ring, the benzisothiazole ring, the benzimidazole ring, more specifically, the 2-thienyl, the 4-pyridine radicals, the 2-furyl, the 2-pyrimidine radicals, the 1-pyridine radicals, the 2-[4-morpholinodithio base, the 1-imidazole radicals, the 1-pyrazolyl, benzotriazole-1-yl), (preferably carbon number is 3～38 to silicyl, the silicyl that more preferably carbon number is 3～18, for example trimethyl silyl, triethylsilyl, the tributyl silicyl, t-butyldimethylsilyl, tertiary hexyl dimetylsilyl), hydroxyl, cyano group, nitro, carboxyl, (preferably carbon number is 1～48 to alkoxy, the alkoxy that more preferably carbon number is 1～24, for example methoxyl, ethoxy, the 1-butoxy, the 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy, cycloalkyloxy (cyclopentyloxy for example, cyclohexyloxy)), (preferably carbon number is 6～48 to aryloxy group, the aryloxy group that more preferably carbon number is 6～24, for example phenoxy group, the 1-naphthoxy), (preferably carbon number is 1～32 to heterocyclic oxy group, the heterocyclic oxy group that more preferably carbon number is 1～18, for example 1-phenyltetrazole-5-oxygen base, the 2-tetrahydro-pyran oxy), (preferably carbon number is 1～32 to siloxy, the siloxy that more preferably carbon number is 1～18, for example trimethylsiloxy, the t-butyldimethylsilyloxy base, the diphenyl methyl siloxy), (preferably carbon number is 2～48 to acyloxy, the acyloxy that more preferably carbon number is 2～24, for example acetoxyl group, new pentane acyloxy, benzoyloxy, dodecane acyl-oxygen base), (preferably carbon number is 2～48 to alkoxy carbonyl oxygen base, the alkoxy carbonyl oxygen base that more preferably carbon number is 2～24, for example ethoxy carbonyl oxygen base, tert-butoxy carbonyl oxygen base, cycloalkyloxy carbonyl oxygen base, for example cyclohexyloxy carbonyl oxygen), (preferably carbon number is 7～32 to aryloxy group carbonyl oxygen base, the aryloxy group carbonyl oxygen base that more preferably carbon number is 7～24, for example phenoxy group carbonyl oxygen base), (preferably carbon number is 1～48 to carbamoyloxy, the carbamoyloxy that more preferably carbon number is 1～24, N for example, N-dimethylamino formyloxy, N-butyl carbamoyloxy, N-phenyl amino formyloxy, N-ethyl-N-phenyl amino formyloxy), (preferably carbon number is 1～32 to sulfamoyloxy, the sulfamoyloxy that more preferably carbon number is 1～24, N for example, N-diethyl amino sulfonyloxy, N-propyl group sulfamoyloxy), (preferably carbon number is 1～38 to alkylsulfonyloxy, the alkylsulfonyloxy that more preferably carbon number is 1～24, for example sulfonyloxy methyl oxygen base, the cetyl sulfonyloxy, the cyclohexyl sulfonyloxy),

(preferably carbon number is 6～32 to aryl-sulfonyl oxygen, the aryl-sulfonyl oxygen that more preferably carbon number is 6～24, phenyl sulfonyloxy for example), (preferably carbon number is 1～48 to acyl group, the acyl group that more preferably carbon number is 1～24, formoxyl for example, acetyl group, valeryl, benzoyl, the myristoyl base, the hexamethylene acyl group), (preferably carbon number is 2～48 to alkoxy carbonyl, the alkoxy carbonyl that more preferably carbon number is 2～24, methoxycarbonyl for example, ethoxy carbonyl, octadecane oxygen base carbonyl, cyclohexyloxy carbonyl, 2, 6-di-t-butyl-4-methyl cyclohexane oxygen base carbonyl),

(preferably carbon number is 7～32 to aryloxycarbonyl, the aryloxycarbonyl that more preferably carbon number is 7～24, for example phenyloxycarbonyl), (preferably carbon number is 1～48 to carbamyl, the carbamyl that more preferably carbon number is 1～24, for example carbamyl, N, N-diethylamino formoxyl, N-ethyl-N-octyl group carbamyl, N, N-dibutylamino formoxyl, N-propyl group carbamyl, N-phenyl amino formoxyl, N-methyl-N-phenyl amino formoxyl, N, N-dicyclohexyl carbamyl), it is amino that (preferably carbon number is below 32, more preferably carbon number is the amino below 24, for example amino, methylamino, N, the N-dibutylamino, tetradecane amino, 2-ethylhexyl amino, cyclohexyl amino), (preferably carbon number is 6～32 to anilino-, the anilino-that more preferably carbon number is 6～24, for example anilino-, the methylphenylamine base), (preferably carbon number is 1～32 to heterocyclic amino group, the heterocyclic amino group that more preferably carbon number is 1～18, for example 4-pyridinylamino), (preferably carbon number is 2～48 to carbonamido, the carbonamido that more preferably carbon number is 2～24, for example acetamido, benzamido, the myristoyl amido, the pivaloyl amido, the cyclohexane amide group), (preferably carbon number is 1～32 to urea groups, the urea groups that more preferably carbon number is 1～24, for example urea groups, N, N-dimethyl urea groups, N-phenyl urea groups), (preferably carbon number is below 36 to imide, more preferably carbon number is the imide below 24, for example the N-succinimide, N phlhalimide), (preferably carbon number is 2～48 to alkoxycarbonyl amino, the alkoxycarbonyl amino that more preferably carbon number is 2～24, for example methoxycarbonyl amino, ethoxy carbonyl amino, tert-butoxycarbonyl amino, octadecane oxygen base carbonylamino, cyclohexyloxy carbonyl amino), aryloxycarbonyl is amino, and (preferably carbon number is 7～32, the aryloxycarbonyl amino that more preferably carbon number is 7～24, for example phenyloxycarbonyl amino), (preferably carbon number is 1～48 to sulfoamido, the sulfoamido that more preferably carbon number is 1～24, for example Methanesulfomide, the fourth sulfonamide, benzsulfamide, the hexadecane sulfonamide, the cyclohexane sulfonamide), sulfamoyl is amino, and (preferably carbon number is 1～48, the sulfamoyl amino that more preferably carbon number is 1～24, N for example, N-dipropyl sulfamoyl amino, N-ethyl-N-dodecyl sulfamoyl amino), (preferably carbon number is 1～32 to azo group, the azo group that more preferably carbon number is 1～24, for example phenylazo, 3-pyrazolyl azo group),

(preferably carbon number is 1～48 to alkylthio group, the alkylthio group that more preferably carbon number is 1～24, for example methyl mercapto, ethylmercapto group, hot sulfenyl, the hexamethylene sulfenyl), (preferably carbon number is 6～48 to arylthio, the arylthio that more preferably carbon number is 6～24, for example thiophenyl), (preferably carbon number is 1～32 to the heterocycle sulfenyl, the heterocycle sulfenyl that more preferably carbon number is 1～18, for example 2-[4-morpholinodithio sulfenyl, the 2-pyridine thio, 1-phenyltetrazole sulfenyl), (preferably carbon number is 1～32 to alkyl sulphinyl, the alkyl sulphinyl that more preferably carbon number is 1～24, for example dodecane sulfinyl), (preferably carbon number is 6～32 to aryl sulfonyl kia, the aryl sulfonyl kia that more preferably carbon number is 6～24, for example phenyl sulfinyl), (preferably carbon number is 1～48 to alkyl sulphonyl, the alkyl sulphonyl that more preferably carbon number is 1～24, for example methyl sulphonyl, ethylsulfonyl, the sulfonyl propyl base, the butyl sulfonyl, the isopropyl sulfonyl, 2-ethylhexyl sulfonyl, the cetyl sulfonyl, the octyl group sulfonyl, the cyclohexyl sulfonyl), (preferably carbon number is 6～48 to aryl sulfonyl, the aryl sulfonyl that more preferably carbon number is 6～24, for example phenyl sulfonyl, 1-naphthyl sulfonyl), (preferably carbon number is below 32 to sulfamoyl, more preferably carbon number is the sulfamoyl below 24, for example sulfamoyl, N, N-dipropyl sulfamoyl, N-ethyl-N-dodecyl sulfamoyl, N-ethyl-N-phenyl sulfamoyl base, N-cyclohexyl sulfamoyl), sulfo group, (preferably carbon number is 1～32 to phosphono, the phosphono that more preferably carbon number is 1～24, for example phenoxy group phosphono, the octyloxy phosphono, the Phenylphosphine acyl group), (preferably carbon number is 1～32 to phosphine acylamino, the phosphine acylamino that more preferably carbon number is 1～24, for example diethoxy phosphonium mesitoyl amino, two octyloxy phosphine acylaminos), or the group that their combinations are obtained.

R in general formula (1-1) ₁₁with R ₁₂, R ₁₂with R ₁₃, R ₁₄with R ₁₅, and/or R ₁₅with R ₁₆can be independently of one another bonding and form saturated rings or the unsaturated ring of 5 yuan, 6 yuan or 7 yuan mutually.When the ring of formed 5 yuan, 6 yuan and 7 yuan during for the group that can further replace, can be by above-mentioned R ₁₁～R ₁₆the substituting group of middle explanation replaces, and when the substituting group by more than 2 replaces, these substituting groups can be the same or different.

R in general formula (1-1) ₁₇mean hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical, R ₁₇halogen atom, alkyl, aryl and heterocyclic radical and above-mentioned R ₁₁～R ₁₆the halogen atom of middle explanation, alkyl, aryl and heterocyclic radical definition are identical.Work as R ₁₇alkyl, aryl, and heterocyclic radical during for the group that can further replace, can be by above-mentioned R ₁₁～R ₁₆the substituting group of middle explanation replaces, and when the substituting group by more than 2 replaces, these substituting groups can be the same or different.

In general formula (1-1) preferably, R ₁₁and R ₁₆mean independently respectively hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, silicyl, hydroxyl, cyano group, alkoxy, aryloxy group, heterocyclic oxy group, acyl group, alkoxy carbonyl, carbamyl, amino, anilino-, heterocyclic amino group, carbonamido, urea groups, imide, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfoamido, azo group, alkylthio group, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl, phosphine acylamino or the group that their combinations are obtained, R ₁₂and R ₁₅mean independently respectively hydrogen atom, halogen atom, alkyl, alkenyl, aryl, heterocyclic radical, hydroxyl, cyano group, nitro, alkoxy, aryloxy group, heterocyclic oxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, imide, alkoxycarbonyl amino, sulfoamido, azo group, alkylthio group, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl or the group that their combinations are obtained, R ₁₃and R ₁₄mean independently respectively hydrogen atom, halogen atom, alkyl, alkenyl, aryl, heterocyclic radical, silicyl, hydroxyl, cyano group, alkoxy, aryloxy group, heterocyclic oxy group, acyl group, alkoxy carbonyl, carbamyl, anilino-, carbonamido, urea groups, imide, alkoxycarbonyl amino, sulfoamido, azo group, alkylthio group, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl, phosphine acylamino or the group that their combinations are obtained, R ₁₇mean hydrogen atom, alkyl, aryl or heterocyclic radical.

More preferably, in above-mentioned general formula (1-1), R ₁₁and R ₁₆mean independently respectively hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, cyano group, acyl group, alkoxy carbonyl, carbamyl, amino, heterocyclic amino group, carbonamido, urea groups, imide, alkoxycarbonyl amino, aryloxycarbonyl amino, sulfoamido, azo group, alkyl sulphonyl, aryl sulfonyl, phosphine acylamino or the group that their combinations are obtained, R ₁₂and R ₁₅mean independently respectively alkyl, alkenyl, aryl, heterocyclic radical, cyano group, nitro, acyl group, alkoxy carbonyl, aryloxycarbonyl, carbamyl, imide, alkyl sulphonyl, aryl sulfonyl, sulfamoyl or the group that their combinations are obtained, R ₁₃and R ₁₄mean independently respectively hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, cyano group, acyl group, alkoxy carbonyl, carbamyl, carbonamido, urea groups, imide, alkoxycarbonyl amino, sulfoamido, alkylthio group, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl or the group that their combinations are obtained, R ₁₇mean hydrogen atom or alkyl.

Particularly preferably be, in general formula (1-1), R ₁₁and R ₁₆mean independently respectively hydrogen atom, alkyl, aryl, heterocyclic radical, amino, heterocyclic amino group, carbonamido, urea groups, imide, alkoxycarbonyl amino, sulfoamido, azo group, alkyl sulphonyl, aryl sulfonyl, phosphine acylamino or the group that their combinations are obtained, R ₁₂and R ₁₅mean independently respectively alkyl, aryl, heterocyclic radical, cyano group, acyl group, alkoxy carbonyl, carbamyl, alkyl sulphonyl, aryl sulfonyl or the group that their combinations are obtained, R ₁₃and R ₁₄mean independently respectively hydrogen atom, alkyl, aryl, heterocyclic radical or the group that their combinations are obtained, R ₁₇mean hydrogen atom.

Ma in general formula (1-1) means metallic atom or metallic compound.As metallic atom or metallic compound, so long as can form metallic atom or the metallic compound of complex compound, get final product, comprise the metallic atom of divalent, the metal oxide of divalent, the metal hydroxides of divalent or the metal chloride of divalent.Such as except Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe etc., also comprise AlCl, InCl, FeCl, TiCl ₂, SnCl ₂, SiCl ₂, GeCl ₂deng metal oxide, Si (OH) such as metal chloride, TiO, VO ₂deng metal hydroxides.

Wherein, from the stability of complex compound, dichroism, thermotolerance, photostability, and manufacture the viewpoint such as adaptability, be preferably Fe, Zn, Co, V=O or Cu, most preferably be Zn.

X in general formula (1-1) ₁so long as can for example, get final product with the group (hydroxyl, carboxylic acid group, phosphate, sulfonic group etc.) of metallic atom Ma bonding, particularly, can enumerate the compound of putting down in writing in the flat work of wild scenery (nineteen ninety-five Nan Jiangtang), " metal-chelator " [2] (1996), " metal-chelator " [3] (1997) etc. on water outlet, alcohols (such as methyl alcohol, ethanol, propyl alcohol), carboxylic acids (such as acetic acid) etc. and " metal-chelator " [1] slope mouth force one.

X in general formula (1-1) ₂expression is used for the required group of electric charge with Ma, such as listing halogen atom, hydroxyl, carboxylic acid group, phosphate, sulfonic group etc.In addition, the compound (for example water, alcohols, carboxylic acids (acetic acid)) that there is this group also can with the Ma bonding.

X in general formula (1-1) ₁with X ₂bonding and form the ring of 5 yuan, 6 yuan or 7 yuan together with Ma mutually.The ring of formed 5 yuan, 6 yuan and 7 yuan can be saturated rings, can be also unsaturated ring.In addition, 5 yuan, 6 yuan and 7 rings can only consist of carbon atom, also can form and at least have 1 heterocycle that is selected from the atom in nitrogen-atoms, oxygen atom and/or sulphur atom.

Dyestuff shown in<general formula (1-2) >

Below, each substituting group of the dyestuff shown in mutual-through type (1-2) is described in detail.

General formula (1-2)

In general formula (1-2), R ₁₂～R ₁₅mean independently respectively hydrogen atom or substituting group.R ₁₇mean hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical.Ma means metallic atom or metallic compound.X ₃mean that (R means hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl to NR.), nitrogen-atoms, oxygen atom or sulphur atom, X ₄mean that (Ra means hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl to NRa.), oxygen atom or sulphur atom, Y ₁mean that (Rc means hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl to NRc.), nitrogen-atoms or carbon atom, Y ₂mean nitrogen-atoms or carbon atom.R ₁₈and R ₁₉mean independently respectively alkyl, alkenyl, aryl, heterocyclic radical, alkoxy, aryloxy group, alkyl amino, arylamino or heterocyclic amino group.R ₁₈with Y ₁bonding and form the ring of 5 yuan, 6 yuan or 7 yuan, R mutually ₁₉with Y ₂bonding and form the ring of 5 yuan, 6 yuan or 7 yuan mutually.X ₅expression can with the group of Ma bonding, a means 0,1 or 2.

R in general formula (1-2) ₁₂～R ₁₅and R ₁₇respectively with general formula (1-1) in R ₁₂～R ₁₅and R ₁₇define identical.

Ma in general formula (1-2) means metallic atom or metallic compound, identical with metallic atom or the metallic compound definition of explanation in general formula (1-1), and its preferred scope is also identical.

In general formula (1-2), R ₁₈and R ₁₉mean independently that respectively (preferably carbon number is 1～36 to alkyl, the straight chain that more preferably carbon number is 1～12, side chain, or the alkyl of ring-type, for example methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, hexyl, the 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, the 1-adamantyl), (preferably carbon number is 2～24 to alkenyl, the alkenyl that more preferably carbon number is 2～12, for example vinyl, allyl, 3-butene-1-yl), (preferably carbon number is 6～36 to aryl, the aryl that more preferably carbon number is 6～18, for example phenyl, naphthyl), (preferably carbon number is 1～24 to heterocyclic radical, the heterocyclic radical that more preferably carbon number is 1～12, for example 2-thienyl, the 4-pyridine radicals, the 2-furyl, the 2-pyrimidine radicals, the 1-pyridine radicals, the 2-[4-morpholinodithio base, the 1-imidazole radicals, the 1-pyrazolyl, benzotriazole-1-yl), (preferably carbon number is 1～36 to alkoxy, the alkoxy that more preferably carbon number is 1～18, for example methoxyl, ethoxy, propoxyl group, butoxy, own oxygen base, the 2-ethyl hexyl oxy, dodecyloxy, cyclohexyloxy), (preferably carbon number is 6～24 to aryloxy group, the aryloxy group that more preferably carbon number is 1～18, for example phenoxy group, naphthoxy), (preferably carbon number is 1～36 to alkyl amino, the alkyl amino that more preferably carbon number is 1～18, for example methylamino, ethylamino, propyl group amino, butyl amino, hexyl amino, 2-ethylhexyl amino, isopropylamino, tert-butyl group amino, tertiary octyl group amino, cyclohexyl amino, N, the N-diethylamino, N, N-dipropyl amino, N, the N-dibutylamino, N-methyl-N-ethylamino), (preferably carbon number is 6～36 to arylamino, the arylamino that more preferably carbon number is 6～18, for example phenyl amino, naphthyl amino, N, the N-diphenyl amino, N-ethyl-N-phenyl amino), (preferably carbon number is 1～24 to heterocyclic amino group, the heterocyclic amino group that more preferably carbon number is 1～12, for example 2-amino-pyrroles, the 3-amino-pyrazol, PA, the 3-aminopyridine), or the group that their combinations are obtained.

In general formula (1-2), work as R ₁₈and R ₁₉when shown alkyl, alkenyl, aryl, heterocyclic radical, alkoxy, aryloxy group, alkyl amino, arylamino and heterocyclic amino group are the group that can further replace, can be by the R of above-mentioned general formula (1-1) ₁₁～R ₁₆shown substituting group replaces, and when the substituting group by more than 2 replaces, these substituting groups can be the same or different.

In general formula (1-2), X ₃mean NR, nitrogen-atoms, oxygen atom or sulphur atom, X ₄mean NRa, oxygen atom or sulphur atom.R and Ra mean respectively hydrogen atom independently, (preferably carbon number is 1～36 to alkyl, the straight chain that more preferably carbon number is 1～12, side chain, or the alkyl of ring-type, for example methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, hexyl, the 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, the 1-adamantyl), (preferably carbon number is 2～24 to alkenyl, the alkenyl that more preferably carbon number is 2～12, for example vinyl, allyl, 3-butene-1-yl), (preferably carbon number is 6～36 to aryl, the aryl that more preferably carbon number is 6～18, for example phenyl, naphthyl), (preferably carbon number is 1～24 to heterocyclic radical, the heterocyclic radical that more preferably carbon number is 1～12, for example 2-thienyl, the 4-pyridine radicals, the 2-furyl, the 2-pyrimidine radicals, the 1-pyridine radicals, the 2-[4-morpholinodithio base, the 1-imidazole radicals, the 1-pyrazolyl, benzotriazole-1-yl), (preferably carbon number is 1～24 to acyl group, the acyl group that more preferably carbon number is 2～18, for example acetyl group, valeryl, the 2-ethylhexyl, benzoyl, the hexamethylene acyl group), (preferably carbon number is 1～24 to alkyl sulphonyl, the alkyl sulphonyl that more preferably carbon number is 1～18, for example methyl sulphonyl, ethylsulfonyl, the isopropyl sulfonyl, the cyclohexyl sulfonyl), (preferably carbon number is 6～24 to aryl sulfonyl, the aryl sulfonyl that more preferably carbon number is 6～18, for example phenyl sulfonyl, the naphthyl sulfonyl).

Alkyl shown in R and Ra, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl, aryl sulfonyl can be further by the R of above-mentioned general formula (1-1) ₁₁～R ₁₆shown substituting group replaces, and when being replaced by a plurality of substituting groups, these substituting groups can be the same or different.

In general formula (1-2), Y ₁mean NRc, nitrogen-atoms or carbon atom, Y ₂mean nitrogen-atoms or carbon atom.Rc and above-mentioned X ₃r definition identical.

In general formula (1-2), R ₁₈with Y ₁bonding mutually, thereby R ₁₈, Y ₁for example, for example, for example, and carbon atom forms 5 rings (cyclopentane, pyrrolidine, tetrahydrofuran, dioxolanes, thiophane, pyrroles, furans, thiophene, indoles, coumarone, benzothiophene), 6 rings (cyclohexane, piperidines, piperazine, morpholine, oxinane, diox, thia cyclohexane (pentamethylene sulphur), dithiane, benzene, piperidines, piperazine, pyridazine, quinoline, quinazoline) or 7 rings (cycloheptane, hexamethylene imine) together.

In general formula (1-2), R ₁₉with Y ₂bonding mutually, thereby R ₁₉, Y ₂and carbon atom forms the ring of 5 yuan, 6 yuan or 7 yuan together.Formed 5 yuan, 6 yuan and 7 rings can list from the R by above-mentioned ₁₈and Y ₁and in the ring that forms of carbon atom, 1 key is become to two keys and the ring that obtains.

R in general formula (1-2) ₁₈with Y ₁, and R ₁₉with Y ₂bonding and 5 yuan, 6 yuan of forming and 7 rings, can be by the R of above-mentioned general formula (1-1) during for the ring that can further replace ₁₁～R ₁₆shown substituting group replaces, and when the substituting group by more than 2 replaces, these substituting groups can be the same or different.

In general formula (1-2), X ₅expression can with the group of Ma bonding, can list with above-mentioned general formula (1-1) in X ₁identical group.A means 0,1 or 2.

As the preferred mode of the compound shown in general formula (1-2), R ₁₂～R ₁₅, R ₁₇and Ma is respectively the preferred mode of putting down in writing in the explanation of the dyestuff shown in general formula (1-1), X ₃for NR (R is hydrogen atom, alkyl), nitrogen-atoms or oxygen atom, X ₄for NRa (Ra is hydrogen atom, alkyl, heterocyclic radical) or oxygen atom, Y ₁for NRc (Rc is hydrogen atom or alkyl), nitrogen-atoms or carbon atom, Y ₂for nitrogen-atoms or carbon atom, X ₅for being situated between by the group of oxygen atom bonding, R ₁₈and R ₁₉be alkyl, aryl, heterocyclic radical, alkoxy or alkyl amino independently respectively, or R ₁₈with Y ₁mutually bonding and form 5 yuan or 6 rings, or R ₁₉with Y ₂mutual bonding and form 5 yuan or 6 rings, a means 0 or 1.

As the preferred mode of the compound shown in general formula (1-2), R ₁₂～R ₁₅, R ₁₇, Ma is respectively the particularly preferred mode of putting down in writing in the explanation of the dyestuff shown in general formula (1-1), X ₃and X ₄for oxygen atom, Y ₁for NH, Y ₂for nitrogen-atoms, X ₅for being situated between by the group of oxygen atom bonding, R ₁₈and R ₁₉be alkyl, aryl, heterocyclic radical, alkoxy or alkyl amino independently respectively, or R ₁₈with Y ₁mutual bonding and form 5 yuan or 6 rings, in addition, R ₁₉with Z ₂mutual bonding and form 5 yuan or 6 rings, a means 0 or 1.

Dyestuff shown in<general formula (1-3) >

Below, each substituting group of the dyestuff shown in mutual-through type (1-3) is described in detail.

General formula (1-3)

In general formula (1-3), R ₁₁～R ₁₆mean independently respectively hydrogen atom or substituting group.R ₁₇mean hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical.Ma means metallic atom or metallic compound.

R in general formula (1-3) ₁₁～R ₁₇respectively with general formula (1-1) in R ₁₁～R ₁₇define identically, preferred mode is also identical.

Ma in general formula (1-3) means metallic atom or metallic compound, identical with metallic atom or the metallic compound definition of explanation in general formula (1-1), and its preferred scope is also identical.

Below, the object lesson of the dyestuff shown in general formula (1-1)～general formula (1-3) below is shown, but the present invention is not limited to these examples.In addition, as other object lesson, can list the middle dyestuff of putting down in writing in paragraph [0058]～[0074] of Japanese Patent Application 2008-149467 instructions etc.

Dyestuff shown in general formula (1-1)～general formula (1-3) can pass through United States Patent (USP) the 4th, 774, No. 339, United States Patent (USP) the 5th, 433, No. 896, No. 2001-240761, TOHKEMY, No. 2002-155052, TOHKEMY, No. 3614586th, Jap.P., Aust.J.Chem, 1965,11,1835-1845, J.H.Boger etc., Heteroatom Chemistry, Vol.1, in No.5 (1990) etc., the method for record is synthesized.

Dyestuff shown in<general formula (3) >

Solidification compound of the present invention can also contain the dyestuff shown in general formula (3) (cyanine based dye).By by this dyestuff and above-mentioned two pyrroles's methylene based dye use, can make the colored pixels of the blueness of form and aspect, brightness, thermotolerance, chemical proofing excellence.

General formula (3)

In general formula (3), R ¹mean independently respectively hydrogen atom or substituting group.

As R ¹shown " substituting group ", so long as the group that can replace gets final product, for example can list aliphatic group (alkyl, alkenyl, alkynyl that preferably total carbon atom number is 1～15.Such as listing methyl, ethyl, vinyl, allyl, ethinyl, isopropenyl, 2-ethylhexyl etc.), (preferably total carbon atom number is 6～16, and more preferably total carbon atom number is 6～12 for halogen atom (fluorine atom, chlorine atom, bromine atoms etc.), aryl.For example can list phenyl, 4-nitrobenzophenone, 2-nitrobenzophenone, 2-chlorphenyl, 2,4-dichlorophenyl, 2,4-3,5-dimethylphenyl, 2-aminomethyl phenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-methoxycarbonyl-4-nitrobenzophenone etc.), (preferably total carbon atom number is 3～15 to heterocyclic radical, and more preferably total carbon atom number is 3～10.Such as listing 3-pyridine radicals, 2-pyridine radicals, 2-pyrimidine radicals, 2-pyrazinyl, 1-piperidyl etc.), (preferably total carbon atom number is 1～16, and more preferably total carbon atom number is 1～12 for cyano group, carboxyl, carbamyl.Such as listing carbamyl, formyl-dimethylamino, diethylamino formoxyl, N-methyl-N-propyl group carbamyl, N-ethyl-N-methoxy ethyl carbamyl, two (2-methyl butyl) carbamyl, two (2-ethylhexyl) carbamyl, two (methoxy ethyl) carbamyl, two (ethoxyethyl group) carbamyl, two (propoxyl group ethyl) carbamyl, N-ethyloic-N-methylamino formoxyl etc.)、

(preferably total carbon atom number is 2～16 to aliphatics oxygen base carbonyl, and more preferably total carbon atom number is 2～10.Such as listing methoxycarbonyl, butoxy carbonyl etc.), (preferably total carbon atom number is 7～17 to aryloxycarbonyl, and more preferably total carbon atom number is 7～15.Such as listing phenyloxycarbonyl etc.), (preferably total carbon atom number is 2～15 to acyl group, and more preferably total carbon atom number is 2～10.Such as listing acetyl group, valeryl, benzoyl etc.), (preferably total carbon atom number is 1～12, and more preferably total carbon atom number is 1～10 for hydroxyl, aliphatics oxygen base.Such as listing methoxyl, ethoxy ethoxy, methoxy ethoxy, methoxyl diethoxy, phenoxy group ethoxy, thio phenyl oxygen base oxethyl etc.), (preferably total carbon atom number is 6～18 to aryloxy group, and more preferably total carbon atom number is 6～14.Such as listing phenoxy group, 4-methylphenoxy etc.), (preferably total carbon atom number is 2～14 to acyloxy, and more preferably total carbon atom number is 2～10.Such as listing acetoxyl group, methoxyl acetoxyl group, benzoyloxy etc.), (preferably total carbon atom number is 1～16 to carbamoyloxy, and more preferably total carbon atom number is 1～10.For example can list dimethylamino formyloxy, diisopropylaminoethyl formoxyl, N, two (the methoxy ethyl)-carbamyls of N-, N, two (the ethoxyethyl group)-carbamyls of N-etc.), (preferably total carbon atom number is 1～15 to heterocyclic oxy group, and more preferably total carbon atom number is 3～10.Such as listing 3-furans oxygen base, 3-pyridine oxygen base, N-methyl 2-piperidyl oxygen base etc.)、

(preferably total carbon atom number is 2～15 to acyl amino, and more preferably total carbon atom number is 3～12.Such as listing N-methyl acetyl amino, N-ethoxyethyl group benzamido, N-methyl methoxy base acetyl-amino etc.), amino (preferably total carbon atom number is 1～16 to carbamyl, and more preferably total carbon atom number is 1～12.For example can list N, N-dimethylamino formamido group, N-methyl-N-methoxy ethyl carbamyl amino etc.), amino (preferably total carbon atom number is 0～16 to sulfamoyl, and more preferably total carbon atom number is 0～12.For example can list N, N-dimethylamino sulfuryl amino.), (preferably total carbon atom number is 2～15 to aliphatics oxygen base carbonylamino, and more preferably total carbon atom number is 2～10.Such as listing methoxycarbonyl amino, methoxy ethoxy carbonylamino etc.), amino (preferably total carbon atom number is 7～17 to aryloxycarbonyl, and more preferably total carbon atom number is 7～15.Such as listing phenyloxycarbonyl amino, 4-methoxycarbonyl amino etc.), (preferably total carbon atom number is 1～12 to the aliphatics sulfonamido, and more preferably total carbon atom number is 1～8.Such as listing methanesulfonamido, fourth sulfonamido etc.), (preferably total carbon atom number is 6～17 to Arenesulfonyl amino, and more preferably total carbon atom number is 6～15.Such as listing phenyl sulfonamido, 4-aminomethyl phenyl sulfonamido etc.), (preferably total carbon atom number is 1～16 to the aliphatics sulfenyl, and more preferably total carbon atom number is 1～12.Such as listing methyl mercapto, ethylmercapto group, ethoxy ethylmercapto group etc.), (preferably total carbon atom number is 6～22 to arylthio, and more preferably total carbon atom number is 6～14.Such as listing thiophenyl, the tertiary butylthio of 2-etc.), (preferably total carbon atom number is 1～15 to the aliphatics sulfonyl, and more preferably total carbon atom number is 1～8.Such as listing mesyl, fourth sulfonyl, methoxyl ethylsulfonyl etc.)、

(preferably total carbon atom number is 6～16 to aryl sulfonyl, and more preferably total carbon atom number is 6～12.Such as listing benzenesulfonyl, 4-tert-butyl benzene sulfonyl, 4-tosyl, 2-tosyl etc.), (preferably total carbon atom number is 0～16 to sulfamoyl, and more preferably total carbon atom number is 0～12.For example can list sulfamoyl, dimethylamino sulfonyl, N, N-diethyl amino sulfonyl etc.), (preferably total carbon atom number is 2～17 to aliphatics sulfonamido formoxyl, and more preferably total carbon atom number is 2～13.Such as listing the amino formoxyl of sulfonyloxy methyl, butyl sulfonamido formoxyl, 2-methyl butyl sulfonamido formoxyl etc.), (preferably total carbon atom number is 7～21 to the Arenesulfonyl amino formoxyl, and more preferably total carbon atom number is 7～17.Such as listing phenyl sulfonamido formoxyl etc.), (preferably total carbon atom number is 2～17 to aliphatics carbonyl sulfamoyl, and more preferably total carbon atom number is 2～13.Such as listing methyl carbonyl sulfamoyl, butyl carbonyl sulfamoyl, 2-ethylhexyl carbonyl sulfamoyl etc.), (preferably total carbon atom number is 7～21 to the aryl carbonyl sulfamoyl, and more preferably total carbon atom number is 7～17.Such as listing phenylcarbonyl group sulfamoyl etc.), (preferably total carbon atom number is 1～16 to aliphatics sulphonyl sulfamoyl, and more preferably total carbon atom number is 1～12.Such as listing methyl carbonyl sulfamoyl, butyl carbonyl sulfamoyl, 2-ethylhexyl carbonyl sulfamoyl etc.), (preferably total carbon atom number is 6～16 to the arylsulfonyl sulfamoyl, and more preferably total carbon atom number is 6～12.Such as listing phenyl sulphonyl sulfamoyl etc.), sulfo group, imide, heterocycle sulfenyl or group that their combinations are obtained.

As above-mentioned " aliphatic group ", its aliphatics position can be straight chain, side chain or ring-type, also can for saturated and unsaturated in any one, for example comprise alkyl, alkenyl, naphthenic base, cycloalkenyl, can, without replacement, also can be substituted base and replace.In addition, " aryl " can be any one in monocycle and condensed ring, can, without replacement, also can be substituted base and replace." heterocyclic radical " is that its heterocycle position has the group of heteroatoms (for example nitrogen-atoms, sulphur atom, oxygen atom) in ring, can be any one in saturated rings and unsaturated ring, can be also monocycle and condensed ring, can, without replacement, also can be substituted base and replace.

Work as R ¹substituting group during for the group that can further replace, can further there is this substituting group, when the substituting group that has more than 2, these substituting groups can be the same or different.

From effect of the present invention aspect, R ¹most preferably be halogen atom, aliphatic group (alkyl etc.), cyano group, carbamyl, aliphatics oxygen base carbonyl, aryloxycarbonyl, hydroxyl, aliphatics oxygen base, carbamoyloxy, heterocyclic oxy group, aliphatics oxygen base carbonyl oxygen base, carbamyl amino, sulfamoyl amino, aliphatics oxygen base carbonylamino, the aliphatics sulfonamido, Arenesulfonyl amino, the aliphatics sulfenyl, arylthio, the aliphatics sulfonyl, aryl sulfonyl, sulfamoyl, aliphatics sulfonamido formoxyl, the Arenesulfonyl amino formoxyl, aliphatics carbonyl sulfamoyl, the aryl carbonyl sulfamoyl, aliphatics sulphonyl sulfamoyl, the arylsulfonyl sulfamoyl, imide, or the group that their combinations are obtained, more preferably aliphatic group, carbamyl, hydroxyl, aliphatics oxygen base carbonyl, aryloxycarbonyl, aliphatics oxygen base, aliphatics oxygen base carbonyl oxygen base, carbamyl amino, sulfamoyl amino, aliphatics oxygen base carbonylamino, the aliphatics sulfonamido, Arenesulfonyl amino, the aliphatics sulfonyl, aryl sulfonyl, sulfamoyl, aliphatics sulfonamido formoxyl, aliphatics carbonyl sulfamoyl, aliphatics sulphonyl sulfamoyl, imide, or the group that their combinations are obtained, most preferably be carbamyl, hydroxyl, aliphatics oxygen base carbonyl, aliphatics oxygen base, aliphatics oxygen base carbonyl oxygen base, carbamyl amino, aliphatics oxygen base carbonylamino, aryl sulfonyl, aliphatics sulfonamido formoxyl, aliphatics carbonyl sulfamoyl, aliphatics sulphonyl sulfamoyl, imide, the aliphatics sulfonyl, or the group that their combinations are obtained.

In general formula (3), L means respectively aliphatics or aromatic linking group independently.If use these linking groups, the form and aspect brightness of resulting colored pixels is more excellent.In addition, each L can be identical or different.

As the aliphatic linking group shown in L, can also can there is substituting group without replacing, the aliphatic group that preferably total carbon atom number is 1～20, the aliphatic group that more preferably total carbon atom number is 1～15.Such as listing methylene, ethylidene, propylidene, butylidene etc.

As the aromatic linking group shown in L, can also can there is substituting group without replacing, the aromatic group that preferably total carbon atom number is 6～20, the aromatic group that more preferably total carbon atom number is 6～16.Such as listing phenylene, naphthylene etc., most preferably be phenylene.

In addition, when n=0, R ¹with S (sulphur atom) Direct Bonding.

In general formula (3), Z ¹expression forms the necessary non-metallic atom group of 6 ring, 4 Z together with 2 carbon atoms ¹can be the same or different.Formed 6 rings can be any one in aromatic ring or heterocycle, can be also condensed ring, and the ring of condensed ring can further have substituting group.As 6 rings, such as listing phenyl ring, pyridine ring, cyclohexene ring, naphthalene nucleus etc., be preferably phenyl ring.

In general formula (3), M means the metallic atom of 2 hydrogen atoms, divalent, the metal oxide of divalent, the metal hydroxides of divalent or the metal chloride of divalent.As this M, for example can list VO, TiO, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂, SnCl ₂, SiCl ₂, GeCl ₂, Si (OH) ₂, H ₂deng, be preferably the mode of VO, Zn, Mn, Cu, Ni, Co.From effect of the present invention aspect, M is preferably VO, Mn, Co, Ni, Cu, Zn or Mg, and more preferably VO, Co, Cu or Zn, most preferably be Cu.

In general formula (3), m mean independently respectively 1 or 2, m be preferably 2.

N mean independently respectively 0 or 1, n be preferably 1.

P means respectively 1～5 integer independently, is preferably 1～3, more preferably 1.

In the present invention, a plurality of R in molecule ¹can be identical or different respectively.Wherein, preferred R ¹have-OY ,-COOY ,-SO ₃y ,-CON (Y) CO-,-CON (Y) SO ₂-,-SO ₂n (Y) CO-or-SO ₂nH-.Thus, can further improve appearance characteristics and the chemical proofing of resulting colored pixels.

Above-mentioned-OY ,-COOY ,-SO ₃y ,-CON (Y) CO-,-CON (Y) SO ₂-(sulfonamido formoxyl) ,-SO ₂n (Y) CO-(acyl group sulfamoyl) or-SO ₂nH-can be in general formula (3) and linking group L bonding, also can be not by linking group L and with-S (=O) _m-Direct Bonding.Be not situated between by linking group L and-S (=O) _min the situation of-Direct Bonding, R ₁be preferably-OY, preferably with-S (=O) _m-form together with tetraazatetradecane porphyrin ring Direct Bonding-SO ₃y (m=2).

Y means hydrogen atom, metallic atom or conjugate acid.Metallic atom shown in Y can list Li, Na, K, Mg, Ca, is preferably Li, Na, K.As the alkali that forms the conjugate acid shown in Y, can list tertiary amines (for example triethylamine, tripropyl amine (TPA), tri-n-butylamine, diisopropylethylamine, N-methyl piperidine, 4-methyl morpholine), guanidine class (for example guanidine, N, N-diphenylguanidine, 1,3-di-o-tolyl guanidine), pyridines (such as pyridine, 2-picoline) etc.Wherein, be preferably triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-diphenylguanidine, 1,3-di-o-tolyl guanidine.

R ¹, r ², r ³and r ⁴mean independently respectively 0 or 1, r ¹+ r ²+ r ³+ r ⁴be more than 1, r ¹+ r ²+ r ³+ r ⁴be preferably 2～4.In addition, preferred r also ¹, r ², r ³and r ⁴respectively do for oneself 1.

Above-mentioned " S (O) below is shown _m-(L) _n-(R ¹) _p" shown in the example of group.But, in the present invention, be not limited thereto.In addition, in following example, preferably can list T-95, T-97, T-114, T-115, T-117, T-127, T-130.

The object lesson of the dyestuff shown in general formula (3) below is shown, but the present invention is not limited thereto.

Exemplary compounds

Ra

Rb

Exemplary compounds

Ra

Rb

CB-1

T-14

T-14

CB-2

T-14

T-15

CB-3

T-14

T-88

CB-4

T-14

T-99

CB-5

T-14

T-141

CB-6

T-46

T-46

CB-7

T-46

T-49

CB-8

T-46

T-56

CB-9

T-89

T-89

CB-10

T-89

T-88

CB-11

T-89

T-99

CB-12

T-89

T-141

CB-13

T-95

T-95

CB-14

T-95

T-88

CB-15

T-95

T-112

CB-16

T-95

T-15

CB-17

T-95

T-114

CB-18

T-95

T-134

CB-19

T-95

T-141

CB-20

T-96

T-96

CB-21

T-96

T-88

CB-22

T-96

T-99

CB-23

T-96

T-112

CB-24

T-96

T-134

CB-25

T-96

T-135

CB-26

T-96

T-141

CB-27

T-97

T-97

CB-28

T-97

T-15

CB-29

T-97

T-88

CB-30

T-97

T-99

CB-31

T-97

T-112

CB-32

T-97

T-120

CB-33

T-97

T-134

CB-34

T-97

T-141

CB-35

T-115

T-115

CB-36

T-115

T-112

CB-37

T-115

T-118

CB-38

T-115

T-134

CB-39

T-115

T-141

CB-40

T-116

T-116

CB-41

T-116

T-112

CB-42

T-116

T-134

CB-43

T-116

T-141

CB-44

T-130

T-130

CB-45

T-130

T-134

CB-46

T-130

T-141

Compound number

Ra

Compound number

Ra

Compound number

Ra

CC-4

T-89

CC-5

T-95

CC-6

T-96

CC-7

T-97

CC-8

T-115

CC-9

T-116

CC-10

T-130

CC-3

T-89

-

-

In addition, the dyestuff shown in above-mentioned general formula (3) (tetraazatetradecane porphyrin based dye) can synthesize by the method such as record in TOHKEMY 2006-58787 communique, TOHKEMY 2006-124379 communique, TOHKEMY 2006-124679 communique etc.

In ink for inking, the total content of the dyestuff shown in the dyestuff shown in general formula (1-1)～general formula (1-3) and general formula (3) is preferably 1～30 quality % with respect to total ink, more preferably 3～20 quality %.When content is very few, in order to reach the optical density required as color filter, the thickness thickening.Therefore black matrix" also needs to thicken, and is difficult to form black matrix", therefore not preferred.When content is too much, ink viscosity uprises, and is difficult to ejection, and is difficult for being dissolved in solvent, therefore not preferred.

In addition, in solidification compound, dyestuff shown in general formula (1-1)～general formula (1-3) (two pyrroles's methylene based dyes) is not particularly limited with the mass ratio (cyanine dye/bis-pyrroles's methylene based dyes) of the dyestuff (cyanine dye) shown in general formula (3), show the viewpoint of more excellent outward appearance, excellent chemical proofing from resulting colored pixels, its mass ratio is preferably 0.3～4, and more preferably 1～3.

<organic solvent >

Solidification compound contains organic solvent.As organic solvent, as long as meet the dissolubility of each composition, be not particularly limited.

As the object lesson of organic solvent, preferably enumerate water outlet or ester class (such as amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate etc.), ethers (such as diethylene glycol dimethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether etc.), ketone (such as cyclohexanone etc.), aromatic hydrocarbon based (such as dimethylbenzene etc.), alcohols (such as phenmethylol etc.), dicyclohexyl methylamine etc.They can use one kind or two or more and use.

The content of the organic solvent in solidification compound is preferably 30～90 quality % with respect to the solidification compound total amount, more preferably 50～90 quality %.More than 30 quality %, can guarantee to be added drop-wise to the amount of composition in 1 pixel by ink-jet method if, the wetting expansion of the composition in pixel is good.In addition, if below 90 quality %, can guarantee to be used to form one-tenth component beyond the desolventizing of functional membrane (such as pixel etc.) more than ormal weight in composition.Thus, when forming color filter, the composition necessary amount of each pixel can not become too much, for example, when by ink-jet method, to the recess of being divided by next door, giving composition, can suppress printing ink from recess overflow, and adjacent pixel generation colour mixture.

In the present invention, the boiling point of organic solvent used is preferably 130～280 ℃.Wherein, the organic solvent that preferably boiling point is 160～250 ℃, more preferably 180～240 ℃.If boiling point is too low, in face, the shape of pixel is not preferred aspect inhomogeneity.If boiling point is too high, by prebake conditions, remove desolventizing aspect not preferred.In addition, the boiling point of organic solvent refers to the boiling point under pressure 1atm, can be by compound dictionary (Chapman& Hall company) etc. physics value table is known.

<polymerizable monomer >

Solidification compound of the present invention contains polymerizable monomer.By adding polymerizable monomer, thereby make the adaptation of drop and substrate improve.And, can expect the raising of the soundnesses such as the raising of the dispersing uniformity of above-mentioned dyestuff in pixel and weatherability thermotolerance.As this polymerizable monomer, be not particularly limited, such as listing cationically polymerizable monomer and free radical polymerization monomer etc.Wherein, aspect many from various substituent variations, that easily obtain is considered, preferably contains the free radical polymerization monomers such as (methyl) acrylic monomer.

As polymerizable monomer, be preferably the monomer with 2 above polymerizable groups.As polymerizable monomer, as long as can be by active energy ray and/or heat and polymerization reaction take place is not particularly limited, but, from aspects such as film strength and chemical proofings, more preferably there is the monomer of 3 above polymerizable groups.

Wherein, soundness and the more excellent aspect of thermotolerance from resulting colored pixels, be preferably the polyfunctional monomer with 3～6 polymerizable groups.Wherein, the number of polymerizable group is preferably 4～6.If in above-mentioned scope, the difficulty when the permanance of colored pixels, monomer acquired, synthetic aspect preferred.

Kind as above-mentioned polymerizable group, be not particularly limited, and as mentioned above, is particularly preferably acryloxy, methacryloxy.As the object lesson of polymerizable monomer, can list the middle acrylate monomer of putting down in writing of paragraph [0016] of TOHKEMY 2002-371216 communique and " market expectation of reactive monomer " middle monomer of putting down in writing of methacrylate monomers and CMC publication etc.

In addition, be acrylate monomer and methacrylate monomers as (methyl) acrylic monomer, can list the acrylate such as the acrylate of the simple functions such as polyethyleneglycol (methyl) acrylate or methacrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate or methacrylate etc.

The content of above-mentioned polymerizable monomer is preferably 30～80 amount % in the solid constituent of solidification compound, more preferably 40～80 quality %.Therefore if the use amount of polymerizable monomer, in above-mentioned scope, because the polymerization of pixel section is abundant, is difficult for causing the generation of the damage that the deficiency by the film strength of pixel section causes.Here, for the solid constituent of the solidification compound of determining mixing ratio, comprise the whole compositions except desolventizing, aqueous polymerizable monomer etc. is also included within solid constituent.

Giving property of<hydrogen compound >

Solidification compound of the present invention contains giving property of the hydrogen compound with functional group of regulation more than 2.By using this giving property of hydrogen compound, thereby make the dispersiveness of above-mentioned two pyrroles's methylene based dyes in colored pixels improve, can make the colored pixels of form and aspect, brightness, thermotolerance, chemical proofing excellence.

Distance between the functional group in giving property of hydrogen compound is not particularly limited, and in the calculating that utilizes MOPAC, the distance between distance functional group farthest is preferably 1.5～1000 dusts, more preferably 3～300 dusts.If in above-mentioned scope, can take into account other performances such as effect that form and aspect optimization, thermotolerance optimizes and chemical proofing, therefore preferably.

Giving property of hydrogen compound at least has 2 and selects free hydroxyl (OH), carboxyl (COOH), amide group (NHCOR ,-CONHR (R is organic group)), sulfonic group (SO ₃h), phosphonate group (PO ₃h ₂) functional group in the group that forms.In addition, the kind of functional group can be identical, also can be different.In addition, in the situation that 2 functional groups are carboxyl, they can bondings and form acid anhydride (CO-O-CO-).In addition, carboxyl and amide group also can bondings and are formed imide (CO-NH-CO-).

In above-mentioned functional group, the more excellent aspect of form and aspect brightness thermotolerance chemical proofing from resulting colored pixels, be preferably hydroxyl, carboxyl, acid anhydride, imide, more preferably hydroxyl, carboxyl, imide, be particularly preferably hydroxyl, carboxyl.

In addition, giving property of hydrogen compound at least has 2 above-mentioned functional groups.When this functional group is 1, insufficient with the interaction of two pyrroles's methylene based dyes, can't obtain showing the desired stable on heating colored pixels of form and aspect brightness.In addition, the more excellent aspect from effect, be preferably more than 3 as the number of this functional group, more preferably 3～8, is particularly preferably 3～6.In addition, when functional group outnumber 8 the time, poorly soluble in solvent of dyestuff or dyestuff and giving property of hydrogen compound, can't obtain the abundant improvement of the characteristic of colored pixels sometimes.

In addition, about acid anhydride, imide, functional group's number separately is calculated as to 2.

Giving property of hydrogen compound is solid under 25 ℃, 1 atmospheric pressure.Be solid by this compound under this condition, thereby also show sufficient thermotolerance in heat curing process etc., and then contribute to the thermotolerance of the dyestuff in colored pixels to improve.

More specifically, as the fusing point (T of giving property of hydrogen compound _m), be preferably more than 40 ℃, more preferably more than 80 ℃.About the upper limit, be not particularly limited, usually below 230 ℃.In addition, the assay method of fusing point is not particularly limited, and can be measured by known methods such as differential scanning type calorimeters (DSC).

The molecular weight of giving property of hydrogen compound is below 3000.Be preferably more than 80 more preferably 100～1000, more preferably 120～500.If this molecular weight in above-mentioned scope, can obtain the colored pixels of form and aspect brightness thermotolerance chemical proofing excellence.

On the other hand, if molecular weight surpasses 3000, diminish the coating of composition, the ejection stability in ink-jet method, and insufficient with the interaction of above-mentioned two pyrroles's methylene based dyes, and result is the form and aspect brightness thermotolerance chemical proofing that diminishes resulting colored pixels.If molecular weight is too low, this giving property of hydrogen compound volatilization or insufficient with the interaction of above-mentioned two pyrroles's methylene based dyes when manufacturing color filter sometimes, result is the form and aspect brightness thermotolerance chemical proofing that diminishes resulting colored pixels.

As the optimal way of giving property of hydrogen compound, in the pass with above-mentioned functional group number, to fasten, the ratio of molecular weight and functional group's number (molecular weight/functional group's number) is preferably more than 36, and more preferably 40～200, be particularly preferably 42～133.If in above-mentioned scope, can effectively improve the form and aspect brightness thermotolerance of resulting colored pixels.

As other optimal way of giving property of hydrogen compound, can list ratio (molecular weight/functional group's number) shown in general formula (2), molecular weight and functional group's number and be more than 36, under 25 ℃, 1 atmospheric pressure is the compound of solid.

General formula (2)

In general formula (2), A means the organic group of n valency.Wherein, the more excellent aspect of form and aspect brightness thermotolerance chemical proofing from colored pixels, be preferably aliphatic group or aromatic group.In addition, the hydrogen atom of the n in A can be replaced with n the B of functional group.

When A is aliphatic group, can be straight chain shape or a chain, wherein be preferably aliphatic alkyl (aliphatic alkyl that particularly carbon number is 1～3).

As aromatic group, particularly, can list aromatic hydrocarbyl or aromatic heterocycle.Wherein, from the more excellent aspect of form and aspect brightness thermotolerance chemical proofing of colored pixels, the aromatic hydrocarbyl (being preferably phenyl ring, cyclohexyl biphenyl, naphthalene nucleus) that preferably carbon number is 6～18.

As the example of this aromatic group, can list phenyl ring, cyclohexyl biphenyl, naphthalene nucleus, fluorenes ring, anthracene nucleus, phenanthrene ring, thiphene ring, pyrrole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring or quinoxaline ring etc.

In general formula (2), B respectively independently expression-OH base ,-the COOH base ,-the NHCOR base ,-the CONHR base ,-SO ₃the H base ,-PO ₃h ₂base.Wherein, from the more excellent aspect of form and aspect brightness thermotolerance chemical proofing of colored pixels, be preferably-OH base ,-the COOH base ,-the CONHR base, more preferably-OH base ,-the COOH base.B can be identical, also can be different.In addition, R means organic group, alkyl, aryl that preferably carbon number is 1～4.

In addition, 2 adjacent B also can bondings and are formed anhydride group (CO-O-OC-) or carbimide base (CO-NH-CO-).

In general formula (2), n means the integer more than 2.Wherein, from the more excellent aspect of form and aspect brightness thermotolerance chemical proofing of colored pixels, n is preferably more than 3, and more preferably 3～8, be particularly preferably 3～6.

When n is 1, can't obtain as mentioned above effect fully.In addition, when n surpasses 8, poorly soluble in solvent of dyestuff or dyestuff and giving property of hydrogen compound, can't obtain the abundant improvement of the characteristic of colored pixels sometimes.

In addition, in solidification compound, giving property of hydrogen compound can only be used a kind, and also two or more kinds may be used.

As giving property of the hydrogen compound used in the present invention, for example can list 1,2,4-benzenetriol, terephthalic acid (TPA), citric acid, malic acid, diglycolic acid, pyromellitic acid, pyromellitic acid acid anhydride, pyromellitic diimide, (+)-N, N '-diallyl-L-TARTARIC ACID diamides etc.

The content of giving property of hydrogen compound is 0.1～12 quality % with respect to the solidification compound total amount, and more preferably 0.3～8 quality %, be particularly preferably 1～8 quality %.By this content is set in above-mentioned scope, thereby can obtain the colored pixels that shows excellent form and aspect brightness thermotolerance chemical proofing.

When containing quantity not sufficient 0.1 quality %, the form and aspect of resulting colored pixels, brightness, poor heat resistance, when content surpasses 12 quality %, the form and aspect of resulting colored pixels, brightness, thermotolerance and drug resistance are poor.

Quality (the W of giving property of the hydrogen compound in solidification compound ₁) with the gross mass (W of dyestuff shown in general formula (1-1)～general formula (1-3) ₂) mass ratio (W ₂/ W ₁) be preferably 0.05～10, more preferably 0.5～5.If in above-mentioned scope, the form and aspect brightness thermotolerance of resulting colored pixels is more excellent.

Quality (the W of giving property of the hydrogen compound in solidification compound ₁) with the quality (W of polymerizable monomer ₃) mass ratio (W ₃/ W ₁) be preferably 1～50, more preferably 3～20.If in above-mentioned scope, the form and aspect brightness thermotolerance of resulting colored pixels is more excellent.

<surfactant >

Can also use surfactant in solidification compound of the present invention.As the example of surfactant, can list in the paragraph [0021] of Japanese kokai publication hei 7-216276 communique and TOHKEMY 2003-337424 communique, Japanese kokai publication hei 11-133600 communique disclosed surfactant as preferred surfactant.

The content of surfactant is preferably below 5 quality % with respect to the solidification compound total amount, more preferably 0.01～2 quality %.If in above-mentioned scope, can not damage other physical property of composition, can obtain preferred surface tension, from seeing in this respect, be preferred.

<polymerization initiator >

In order to promote the polyreaction of polymerizable monomer, in solidification compound of the present invention, can use polymerization initiator.Polymerization initiator can be selected according to kind, the polymerization path of free radical polymerization monomer used in solidification compound, such as listing thermal polymerization Photoepolymerizationinitiater initiater etc.As polymerization initiator, for example can use the thermal polymerization of putting down in writing in paragraph [0086]～[0117] of Japanese patent application 2007-303656 instructions.

The content of polymerization initiator is preferably 0.01～50 quality % with respect to all solids composition in solidification compound, more preferably 1～30 quality %.If content in above-mentioned scope, can form better sensitivity and solidified portion firmly.

As other adjuvant, can list other adjuvant of record in paragraph [0058]～[0071] of TOHKEMY 2000-310706 communique.

Content as each composition of solidification compound, the more excellent aspect from each characteristic of resulting colored pixels, with respect to total composition, dyestuff shown in dyestuff～general formula (1-3) shown in general formula (1-1) (two pyrroles's methylene based dyes) is preferably 1～30 quality % with the total content of the dyestuff (cyanine based dye) shown in general formula (3), 2～20 quality % more preferably, the content of organic solvent is preferably 30～90 quality %, 50～90 quality % more preferably, the content of polymerizable monomer is preferably 5～50 quality %, 7～30 quality % more preferably, the content of giving property of hydrogen compound is preferably 0.1～12 quality %, 0.3～8 quality % more preferably.

The manufacture of solidification compound of the present invention is not particularly limited, and can be undertaken by known method.For example can be in organic solvent after dissolving dye, then dissolve needed each and become to assign to modulate solidification compound.

The physics value of<solidification compound >

As the physics value of solidification compound of the present invention, as long as, in the scope that can be coated with or can be sprayed by ink gun, be not particularly limited.Wherein, from the viewpoint of coating and the stability that sprays by ink-jet, preferred composition viscosity is below 30mPas under 25 ℃, more preferably 2～30mPas, more preferably 2～20mPas.In addition, while spraying in device, preferably the temperature of solidification compound is remained in the scope of 20～80 ℃ roughly under uniform temperature.If be high temperature by the Temperature Setting of device, the reduced viscosity of solidification compound, can spray more full-bodied composition.

In addition, viscosity for example is, by adopting E type viscosity meter usually used (the E type viscosity meter (RE-80L) that Toki Sangyo Co., Ltd. manufactures is measured the value obtained solidification compound being remained under the state of 25 ℃.

In addition, as the surface tension (static surface tension) under 25 ℃ of solidification compound, aspect from the raising of the wetting state to the impermeability substrate and coating and the stability that sprays by ink-jet, be preferably 20～40mN/m, more preferably 20～35mN/m.In addition, while spraying in device, preferably the temperature of solidification compound is remained in the scope of 20～80 ℃ roughly under uniform temperature, preferably surface tension now is made as to 20～40mN/m.

Above-mentioned surface tension is to adopt surface tensiometer usually used (such as the manufacture of consonance interface science Co., Ltd., surface tensiometer FACE SURFACE TENSIOMETER CBVB-A3 etc.) to measure the value obtained by Wilhelmy (Wilhelmy) method under 25 ℃ of liquid temperatures, 60%RH.

The colored pixels that solidification compound of the present invention can be preferably used as liquid crystal display cells (LCD) and the middle color filter used of solid-state image pickup (such as CCD, CMOS etc.) etc. forms purposes.In addition, can also be preferably used as the making purposes of printing-ink, ink for inking and coating etc.Particularly preferably as ink for inking.

<colored pixels (color image) >

About adopting solidification compound of the present invention by the colourity of the colored pixels (color image, recording materials) of method acquisition described later, in situation about meaning with the CIE-XYZ color specification system that uses illuminant-C mensuration to obtain, when the value on the xy chromatic diagram is made as to 7≤Y (values Y is more than 7), preferably in the scope surrounded by 0.125<x<0.145 and 0.075<y<0.140.More preferably in the scope surrounded by 0.130<x<0.140 and 0.090<y<0.120.

In the XYZ color specification system, color can be by (x, y, Y) these 3 parameters as shown in the formula expression.Now, following x, y mean the parameter of form and aspect and chroma, and X, Y, Z are the colour stimulus values.

(formula W) x=X/ (X+Y+Z), y=Y/ (X+Y+Z)

In addition, the brightness Y value about in the above-mentioned preferable range of form and aspect on the xy chromatic diagram of resulting colored pixels the time, from being applied to the viewpoint of color filter, be preferably more than 7, more preferably, more than 10, is particularly preferably more than 12.

<color filter and manufacture method thereof >

Use the manufacture method of the color filter of solidification compound of the present invention to be not particularly limited, mainly can list ink-jet method and colored resist method.

Below each mode is described in detail.

(ink-jet method)

With reference to preferred implementation shown in the drawings, the manufacture method of the color filter that utilizes ink-jet method is elaborated.

The manufacture method of color filter is characterised in that to have following operation (hereinafter referred to as " pixel formation operation "): the recess next door by being formed on substrate surrounded by ink-jet method is given solidification compound of the present invention (following also referred to as ink for inking of the present invention), thereby forms pixel.Preferably, pixel forms operation and has the operation of describing and curing process, and baking other operations such as processing further are set as required and form, the described operation of describing is that the recess of passing through on substrate being divided in next door by ink-jet method is given solidification compound with the form of drop, described curing process be so that the pixel (solidification compound in recess) of at least a kind of color describing in formation after irradiation or heat by active energy ray be cured, thereby form colored pixels.

Fig. 1 means the process flow diagram of the manufacturing process in the embodiment of manufacture method of color filter of the present invention, and Fig. 2 (a)～(f) is according to the substrate shown in the order of the manufacturing process from substrate to color filter in the manufacture method of color filter of the present invention and the schematic section of color filter.

As shown in Fig. 1 and Fig. 2 (a)～(f), the manufacture method of color filter 10 of the present invention has following operation: form the next door formation operation S102 (with reference to Fig. 2 (b)) as the next door (bank) 14 of black matrix" (BM) on substrate 12; Counter septum 14 is given the lyophoby treatment process S104 of lyophobicity (ink-resistant); Thereby give to the recess 16 between adjacent next door 14 the pixel formation operation S106 (with reference to Fig. 2 (c)～(e)) that ink for inking 18 of the present invention forms colored pixels 20 by ink-jet method; Thereby the diaphragm 22 that is formed for protecting formed colored pixels 20 is manufactured the diaphragm of color filters 10 and is formed operation S108 (with reference to Fig. 2 (f)).

In addition, pixel forms operation S106 and has as mentioned above following operation: the recess 16 by 14 of ink-jet method counter septums with the form of drop, spray and give printing ink 18 describe operation S110 (with reference to Fig. 2 (c)); Thereby the pretreatment process S112 (with reference to Fig. 2 (d)) that makes to be endowed printing ink 18 dryings of recess 16 and remove the solvent formation 18a of the printing ink remnants of defeated troops in removal ink 18; Make the 18a of printing ink remnants of defeated troops polymerization and solidify by the irradiation process of the 18a of the printing ink remnants of defeated troops irradiation active energy ray in the recess 16 on substrate 12 and/or the heating process that the 18a of the printing ink remnants of defeated troops is heated, thus the curing process S114 (with reference to Fig. 2 (e)) of formation colored pixels 20.

In addition, next door 14 is to be pre-formed the parts on substrate 12 in the next door formation operation S102 before pixel forms operation S106, the detailed content that forms operation S102 and forming method thereof about 14 next door, next door is narrated in the back, at first pixel is formed to operation S106 and describes.

<pixel forms operation >

As shown in Fig. 2 (c)～(e), form and to describe operation S110 in operation S106 in pixel, recess 16 by 14 of ink-jet method counter septums (next door of isolation color) is given the drop of ink for inking 18 of the present invention, thereby by curing process S114, given printing ink 18 is solidified and forms pixel 20.This pixel 20 becomes the redness (R) that forms color filter 10, green (G), blue colored pixels such as (B).The ink for inking of the application of the invention, can manufacture the color filter 10 of the colored pixels with blueness (B).In addition, the substrate 12 as color filter, be not particularly limited, and can use the resin plates such as glass plate or polycarbonate, polymethylmethacrylate, polyethylene terephthalate.

As describing the ink-jetting style adopted in operation S110, be not particularly limited, can adopt spray continuously charged ink for inking and utilize method that electric field controlled, use piezoelectric element spray off and on ink for inking method, ink for inking is added to its foaming of heat utilization and the whole bag of tricks such as method that intermittently sprayed.

As used ink gun, can use continuous type or the ink gun (ejecting head) of the variety of way such as piezoelectricity mode, hot mode, solid-state (solid) mode, electrostatic attraction mode of (On Demand) type as required.In addition, the blowing unit of ink gun (nozzle) is not limited to single-row configuration, can be set as the multiple row configuration, also can be set as staggered trellis configuration.

As the color filter that uses ink for inking of the present invention to manufacture, not only can list monochromatic color filter, the color filter of these 3 kinds of colors of colored pixels of the colored pixels of the green (G) that also can list colored pixels with the redness (R) formed by yellow (Y) and magenta (M), by yellow (Y) and cyan (C), is formed, the blueness (B) obtained by solidification compound of the present invention or the color filter etc. of colored pixels of 4～6 kinds of colors that further there is the colored pixels of yellow (Y), magenta (M), cyan (C).

Except ink for inking of the present invention, each the painted printing ink of using as being used to form color filter, can be used the known painted printing ink of using.

Shape for color filter pattern is not particularly limited, and as the black matrix" shape, can be general striated, can be clathrate yet, can also be that triangle (delta) is arranged shape.

In the present invention, also can be as shown in Fig. 2 (c), give the drop of printing ink 18 to the recess 16 on substrate 12 in describing operation S110 and form printing ink 18 the layer after, as shown in Fig. 2 (d), dry except the interior contained organic solvent of removal ink 18 by pretreatment process S112, thereby make the 18a of the printing ink remnants of defeated troops, then as shown in Fig. 2 (e), by the curing process S114 that the 18a of the printing ink remnants of defeated troops irradiated to active energy ray and/or the 18a of the printing ink remnants of defeated troops is heated by the 18a of printing ink remnants of defeated troops polymerization, thereby form pixel 20.

<curing process >

In the manufacture method of color filter of the present invention, can arrange by the irradiation of active energy ray or the curing operation of uncured pixel printing ink 18a of heat desired form and aspect by red (R), green (G) and blue (B) etc.In addition, in order to implement the irradiation of active energy ray, the device of the great numbers such as needs use UV irradiation unit, can cause the maximization of device and the increase of manufacturing cost etc., so preferably utilize heat to be cured.

Ink for inking of the present invention can form by heat curing the colored pixels that shows excellent form and aspect brightness thermotolerance chemical proofing, and the techniques such as irradiation can be set.

Below, the situation of heat curing is described in detail.

In this curing process, the uncured pixel printing ink that forms next door and consist of desired form and aspect, carry out heat treated (so-called baking processing), can utilize heat to implement to solidify.That is, the substrate that is formed with next door and uncured pixel printing ink can be put in electric furnace, exsiccator etc. to be heated or irradiate infrared lamp and heated.

Depend on heating-up temperature and heat time heating time the composition of ink for inking and the thickness of pixel, preferably approximately 120 ℃～approximately heating approximately 10 minutes～approximately 120 minutes under 250 ℃.

In addition, in the manufacture method of the color filter that uses ink for inking of the present invention, utilizing thermal treatment to carry out before pixel forms the polymerization with the printing ink in recess (uncured pixel), as pretreatment process S112, can arranging and preheating operation.The heating-up temperature preheated in operation is not particularly limited, when the temperature that uncured pixel printing ink is started to thermal polymerization is made as T ℃, be preferably lower than T ℃, temperature that can not cause the polymerization of uncured pixel printing ink, more preferably 50～100 ℃, more preferably 60～90 ℃.Originally preheat operation by adding, the evaporation of the organic solvent in the printing ink that can promote to give by ink-jet method, can effectively make color filter, and, because the viscosity of the printing ink remnants of defeated troops reduces because of heat, so can obtain higher mobility, can obtain the color filter of the pixel with high flatness.

Temperature T can as described belowly be tried to achieve.Printing ink is heated, and by heating, printing ink starts polymerization, and the temperature of observing the gelation etc. of printing ink is made as to T.More specifically, by the ink viscosity after heating, the heating-up temperature of 5mPas when above that rise to of the ink viscosity before with respect to heating is made as T.

<next door forms operation >

In the manufacture method of color filter of the present invention, above-mentioned pixel forms in operation S106, as shown in Fig. 2 (c)～(e), the recess 16 next door 14 by being formed on substrate 12 surrounded by ink-jet method is given the drop of ink for inking 18 of the present invention, thereby forms pixel 20.

This next door 14 is not particularly limited, and can use known next door.While making color filter, be preferably the next door with light-proofness that possesses the black matrix" function.

In addition, next door forms in operation S102, as shown in Fig. 2 (b), on the substrate 12 shown in Fig. 2 (a), forms the next door with light-proofness 14 that possesses the black matrix" function.

In addition, in order to prevent the colour mixture of ink for inking, can implement the oleophobic China ink to this next door 14 and process.

Therefore, in the example shown in Fig. 1, after next door forms operation S102, in lyophoby treatment process S104, lyophoby is implemented in the next door 14 on the substrate 12 shown in Fig. 2 (b) and process, be that the oleophobic China ink is processed.In addition, as such oleophobic China ink, process, for example can list the oleophobic China ink disposal route of record in paragraph [0086]～[0087] of TOHKEMY 2007-187884 communique, be particularly preferably the method for implementing to utilize the oleophobic China inkization processing of plasma to being formed at next door on substrate.

As shown in Fig. 2 (e), after forming next door 14 and pixel 20 on substrate 12, making color filter 10, in order to improve permanance, as shown in Fig. 2 (f), can form external coating 22 as protective seam to cover pixel 20 and next door 14 whole.External coating 22 can be protected pixel 20 and the next doors 14 such as R, G, B, and makes to have an even surface.

(colored resist method)

Color filter of the present invention also can be manufactured by colored resist method with above-mentioned solidification compound.Below for colored resist method, be described in detail.

Color filter of the present invention also can be manufactured by the method with following operation: coating in the recess of dividing in the next door by being formed on substrate (for example rotary coating, curtain coating coating, roller coat) solidification compound, Jie carries out pattern exposure by mask, use developer solution to be developed, thereby form pattern image.

Can be not particularly limited by applicable exposure light source, but be preferably the light source with the following wavelength of 400nm.Such as utilizing xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp etc., while only using specific wavelength, also can utilize optical filter.

Can also utilize the ultraviolet rays such as ArF excimer laser (wavelength 193nm), KrF excimer laser (wavelength 248nm), i line (wavelength 365nm).From the viewpoint of cost and exposure energy, particularly preferred exposure light source is ultraviolet ray, can list the i line.

Can also arrange formed pattern is made to its further curing curing process by heating and/or exposure as required.Light or radioactive ray as now using, particularly preferably adopt i line isoradial.

Substrate with recess of dividing by next door can be made by above-mentioned method.

Developer solution as the manufacture method for color filter of the present invention, as long as there is the develop zone (uncured section) of removing and the composition that can not dissolve zone (solidified portion) in addition wanted that can dissolve solidification compound of the present invention, can use any developer solution.Particularly can use the combination of various organic solvents and alkaline aqueous solution.As this organic solvent, the above-mentioned solvent used in the time of can listing modulation composition of the present invention.

Color filter of the present invention can also have tin indium oxide (ITO) layer as nesa coating.Formation method as the ITO layer, such as listing online low temperature sputtering method, online high temperature sputtering method, batch (-type) low temperature sputtering method, batch (-type) high temperature sputtering method, vacuum vapour deposition, reach plasma CVD method etc., especially the low temperature sputtering method is few for the damage of color filter, so preferably use.

As the color filter that possesses the colored pixels (magenta pixel) that makes to contain above-mentioned two pyrroles's methylene based dyes and do not obtain as the solidification compound heat curing of dyestuff containing the cyanine based dye, the color filter that the half breadth that is preferably the maximum absorption band of the optical absorption spectra that this two pyrroles methylene dye is include monochrome pixels is 60nm following (being preferably below 45nm, more preferably 25～40nm).If in above-mentioned scope, brightness is higher, and form and aspect are good, so preferably.

In addition, the peak value (λ of optical absorption spectra _max) be preferably the scope of 535～580nm, the more preferably scope of 545～565nm.

The purposes that color filter of the present invention shows such as image demonstration, the particularly coloured image that can preferably be applicable to without particular limitation the portable terminal devices such as liquid crystal display, TV, personal computer, liquid crystal projection apparatus, game machine, portable phone, digital camera, auto-navigation system etc.

In addition, color filter of the present invention can also be applicable to image display, the particularly color image display apparatus such as Electronic Paper and organic EL equipment.

Embodiment

Below list embodiment the present invention is carried out to more specific description.Material shown in following embodiment, reagent, ratio, instrument, operation etc. only otherwise depart from the scope of the present invention, can suitably be changed.Therefore, scope of the present invention is not limited to object lesson shown below.In addition, in following embodiment, unless otherwise specified, " % " reaches " part " expression " quality % " and reaches " mass parts ", and molecular weight means weight-average molecular weight.

(next door forms the modulation of the heavy colour composition of use)

At first, take K Pigments thing 1, the propylene glycol monomethyl ether of the amount of record in table 1, in the lower mixing of 24 ℃ of temperature (± 2 ℃) and with 150rpm stirring 10 minutes.Stir on one side again, take MEK, bonding agent 2, Hydroquinone monomethylether, the DPHA liquid, 2 of the amount of record in table 1 on one side, two (the trichloromethyl)-6-[4 ' of 4--(N, the two ethoxy carbonyl methyl of N-) amino-3 '-bromophenyl]-s-triazine, surfactant 1, and add successively at 25 ℃ of temperature (± 2 ℃), stir 30 minutes with 150rpm at 40 ℃ of temperature (± 2 ℃), thereby obtain heavy colour composition K1.In addition, in table 1, the amount of record is mass parts, is specifically following composition.

<K Pigments thing 1 >

Carbon black (Nipex35 that Degussa company manufactures) 13.1%

Spreading agent (following compound 1) 0.65%

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

Propylene glycol monomethyl ether 79.53%

Compound 1

<bonding agent 2 >

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand) 27%

Propylene glycol monomethyl ether 73%

<DPHA liquid >

Dipentaerythritol acrylate

(the polymerization inhibitor MEHQ that contains 500ppm, Japanese chemical drug company manufacture, trade name: KAYARAD DPHA) 76%

Propylene glycol monomethyl ether 24%

<surfactant 1 >

Following works 130%

MEK 70%

Works 1

(n＝6、x＝55、y＝5

Mw＝33940、Mw/Mn＝2.55

PO: epoxypropane, EO: oxirane)

Table 1

(mass parts)

(formation in next door)

Alkali-free glass substrate, with after the washing of UV wash mill, is washed by brush with washing agent, then carried out ultrasonic washing with ultrapure water.By substrate 120 ℃ of lower thermal treatments 3 minutes, thereby make the surface state stabilization.

By substrate cooling and adjust the temperature to 23 ℃ after, utilize coating machine glass substrate for slit-shaped nozzle (エ Off エ mono-エ ス ア ジ ア company manufactures, trade name: MH-1600), the heavy colour composition K1 that coating is modulated as mentioned above.Then with 30 seconds of VCD (Minton dryer, Tokyo answer chemical industry company to manufacture) by the partial solvent drying, thereby make the mobility disappearance of coating layer, then 120 ℃ of lower prebake conditions 3 minutes, thereby obtain the heavy colour composition layer K1 that thickness is 2.3 μ m.

With the proximity printing machine with ultrahigh pressure mercury lamp (manufacture of the Ha イ テ of Hitachi Network electronics エ Application ジ ニ ア リ Application グ Co., Ltd.), under the state stood vertically at substrate and mask (the quartzy exposed mask with picture pattern), distance between exposed mask face and heavy colour composition layer K1 is set as to 200 μ m, under blanket of nitrogen, take exposure as 300mJ/cm ²according to the next door width, be that 20 μ m, interval width are that 100 μ m carry out pattern exposure.

Then, with the spray spout pure water of spraying, after the surface uniform of heavy colour composition layer K1 is got wet, with KOH be developer solution (will contain 100 times of non-ionic surfactant, trade name: CDK-1, the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ Co., Ltd. goods dilutions and obtain developer solution) under 23 ℃, take flat burner pressure as 0.04MPa carry out 80 seconds spray develop, obtain the patterning image.Then, the pressure injection ultrapure water by the UHV (ultra-high voltage) Washing spray nozzle with 9.8MPa, carry out residue and remove, and take exposure as 2500mJ/cm under atmosphere ²carry out post-exposure from the face side that is formed with heavy colour composition layer K1 of substrate, utilize baking oven to heat 50 minutes under 240 ℃, to obtain thickness and be 2.0 μ m, optical density be 4.0, have the next door of the striated of the wide peristome of 100 μ m.

(oleophobic China inkization Cement Composite Treated by Plasma)

For forming septate substrate, adopt negative electrode coupling mode parallel plate-type plasma processing apparatus, carry out under the following conditions oleophobic China inkization Cement Composite Treated by Plasma.

Use gas: CF ₄

Gas flow: 80sccm

Pressure: 40Pa

RF power: 50W

Processing time: 30sec

Printing ink and magenta ink for<blue (B) >

Following composition is mixed with the mixing ratio of record in table 2 and table 3, stir 1 hour.Then, the micro-strainer that is 0.25 μ m by average pore size carries out filtration under diminished pressure, thereby is modulated into blue with printing ink liquid and magenta ink.

As follows by the detailed content of each material of printing ink and magenta ink for modulating blueness (B).

(organic solvent)

Cyclohexanone (with the pure medicine manufacture of light)

1-METHYLPYRROLIDONE (with the pure medicine manufacture of light)

1,3-BGDA (manufacture: the 1,3-BDO diacetate esters) (monomer) by Daicel chemical industry

DPHA (Japanese chemical drug company's manufacture (KAYARAD DPHA))

: dipentaerythritol acrylate

DPCA-60 (Japanese chemical drug company's manufacture (KAYARAD DPCA-60))

: caprolactone modification dipentaerythritol acrylate

(surfactant)

(the シ リ コ of SHIN-ETSU HANTOTAI mono-Application company manufactures KF-353: polyether modified silicon oil)

F781-F (manufacture: Megafac F781F) by large Japanese ink chemical industry

(polymerization initiator)

IRGACURE 819 (Xiba Special Chemical Product Co.,Ltd's manufacture)

IRGACURE OXE 02 (Xiba Special Chemical Product Co.,Ltd's manufacture)

(giving property of hydrogen compound)

1,2,4-benzenetriol (OH base, functional group's number: 3)

Terephthalic acid (TPA) (COOH base, functional group's number: 2)

Citric acid (the COOH base ,-OH base, functional group's number: 4)

Pyromellitic acid (COOH base, functional group's number: 4)

Pyromellitic acid acid anhydride (anhydride group, functional group's number: 4)

Pyromellitic diimide (imide, functional group's number: 4)

DATdAm:(+)-N, N '-diallyl-L-TARTARIC ACID diamides (OH base, amide group, functional group's number: 4)

(other adjuvants: comparative example is used)

Pyromellitic acid tetramethyl ester (4 yuan of carboxylates)

Benzoic acid (1 yuan of carboxylic acid)

BT (3 yuan alcohol, room temperature liquid)

(dyestuff)

Particular dye C-1 (the exemplary compounds CA-19 of the dyestuff shown in above-mentioned general formula (3))

Particular dye C-2 (the exemplary compounds CC-05 of the dyestuff shown in above-mentioned general formula (3))

Particular dye C-3 (the exemplary compounds CB-34 of the dyestuff shown in above-mentioned general formula (3).In addition, T-97 and T-141 mean above-mentioned illustrative functional group.)

Particular dye M-1 (the exemplary compounds I-21 of the dyestuff shown in above-mentioned general formula (1-2))

Particular dye M-2 (the exemplary compounds III-58 of the dyestuff shown in above-mentioned general formula (1-2))

Particular dye M-3 (the exemplary compounds I-2 of the dyestuff shown in above-mentioned general formula (1-1))

Particular dye M-4 (the exemplary compounds Ia-35 of the dyestuff shown in above-mentioned general formula (1-3))

Particular dye M-5 (the exemplary compounds III-1 of the dyestuff shown in above-mentioned general formula (1-2))

<utilize the manufacture of the color filter of ink-jet method >

Use the solidification compound of the B-1 of above-mentioned modulation, the ink-jet printer DMP-2831 that adopts Fujiphoto Dimatix company to manufacture is sprayed (recess surrounded by protuberance) in the zone of being distinguished by next door on substrate obtained above, then, carry out heating in 2 minutes in 100 ℃ of baking ovens.

Then, by the baking oven at 220 ℃ standing 30 minutes, thereby make monochromatic color filter.The thickness of resulting colored pixels is 2.0 μ m.

In addition, for other B-2～B-12, B relatively-1～B relatively-8, and each solidification compound of M-1～M-12, also by same method making color filter.

<utilize the manufacture of the color filter of colored resist method >

On the substrate with recess obtained above, be coated with the solidification compound of the B-1 of above-mentioned modulation, make the dry film thickness of coated film reach 2.2 μ m, form the coated film of solidifying property.Then, carry out 120 heat treated in second (prebake conditions) with the hot plate of 100 ℃.Then, use i line stepping exposure device FPA-3000i5+ (Canon Co., Ltd. system), the island-shaped pattern mask that is 180 μ m * 450 μ m four directions by pattern under the wavelength of 365nm is with 2000mJ/cm ²irradiated.Then, will be formed with the substrate-placing of the coated film through irradiating in rotary spraying type developing machine (DW-30 type; Chemitronics Co., Ltd. manufactures) horizontal rotating table on, carry out infiltration (puddle, the puddle) development in 60 seconds under 23 ℃ with MEK, make monochromatic color filter.

In addition, for other B-2～B-12, B relatively-1～B relatively-8, and each solidification compound of M-1～M-12, also by same method making color filter.

<viscosity, capillary mensuration >

Measure viscosity and the surface tension of the solidification compound of above-mentioned modulation.

By the adjustment to 25 of solidification compound ℃, the E type viscosity meter (RE-80L) that uses Toki Sangyo Co., Ltd. to manufacture under this state, the viscosity of mensuration solidification compound under following condition.Show the result in table 2 and table 3.

(condition determination)

Use rotor: 1 ° of 34 ' * R24

Minute: 2 minutes

Measure temperature: 25 ℃

By the adjustment to 25 of solidification compound ℃, the surface tensiometer (FACE SURFACE TENSIOMETER CBVB-A3) that uses consonance interface science Co., Ltd. to manufacture under this state is measured surface tension.Show the result in table 2 and table 3.

<form and aspect >

Form and aspect about the monochromatic color filter by above-mentioned ink-jet method making, when light source is used illuminant-C, if in the scope (scope A) of 0.130<x<0.140 and 0.090<y<0.120 be made as ◎, if be not included in this scope A but in the scope of 0.125<x<0.145 and 0.075<y<0.140 be made as zero, if in scope in addition be made as *.The mensuration of form and aspect is used UV-560 (Japanese light splitting company manufacture).Show the result in following table 4.

<brightness >

When light source is used illuminant-C, the form and aspect of the monochromatic color filter of making by above-mentioned ink-jet method are in the situation that in the scope of 0.125<x<0.145 and 0.075<y<0.140, by the value of brightness Y now, be the ◎ that is made as more than 12, by the value of brightness Y less than 12 and be to be made as zero more than 10, by the value of brightness Y less than 10 and be the △ that is made as more than 7, by the value of brightness Y less than 7 be made as *.The mensuration of brightness is used UV-560 (Japanese light splitting company manufacture).Show the result in following table 4.

<Evaluation of Heat Tolerance >

The monochromatic color filter that to make by above-mentioned ink-jet method is put in the baking oven that is heated to 220 ℃ or 235 ℃, after placing 1 hour, measures form and aspect.The mensuration of form and aspect is used UV-560 (Japanese light splitting company manufacture), by the Δ Eab before and after estimating lower than 3 the ◎ that is made as.By Δ Eab be more than 3 and lower than 7 be made as zero, by Δ Eab, be more than 7 and lower than 15 the △ that is made as, by Δ Eab be being made as more than 15 *.Show the result in following table 4.

In addition, Δ Eab is the value of utilizing CIE1976 (L*, a*, b*) spatial table colour system to be tried to achieve by following colour difference formula (Japanese color science can be compiled newly organized color science handbook (clear and 60 years) p.266).

ΔEab＝{(ΔL) ²+(Δa) ²+(Δb) ²} ^1/2

<chemical proofing evaluation >

The monochromatic color filter that to make by above-mentioned ink-jet method floods 20 minutes in the chemicals of being estimated (1-METHYLPYRROLIDONE, ethanol), measures the form and aspect of its front and back.The mensuration of form and aspect is used UV-560 (Japanese light splitting company manufacture), by Δ Eab lower than 3 the ◎ that is made as.By Δ Eab be more than 3 and lower than 7 be made as zero, by Δ Eab, be more than 7 and lower than 15 the △ that is made as, by Δ Eab be being made as more than 15 *.Show the result in following table 4.

<half breadth >

Used the absorption spectrum of the color filter of the magenta ink of making by above-mentioned ink-jet method to utilize ultraviolet-visible pectrophotometer (Japan Spectroscopy Corporation's manufacture, trade name " V-560 ") to be measured.According to the absorption spectrum recorded, obtain the half breadth of maximum absorption band.Be that situation below 45nm is made as ◎ by half breadth, will be made as zero over 45nm and the following situation of 50nm, the situation that will surpass below 50nm and 60nm be made as △, will be made as over the situation of 60nm *.Show the result in table 5.

In evaluation result in following table 4 and table 5, the viewpoint of using from practicality, must not comprise *.

From table 4 and 5, use solidification compound of the present invention, the optical characteristics excellences such as the form and aspect of the colored pixels obtained by heat curing process and brightness, and thermotolerance and chemical proofing are also excellent.In addition, in the monochromatic color filter of making by colored resist method, also obtained the evaluation of " form and aspect " " brightness " " thermotolerance " " chemical proofing " same with the monochromatic color filter of making by ink-jet method.

Wherein, according to relatively can the confirming of B-5, B-8 and B-9, by using the dyestuff shown in general formula (1-2), thereby obtained, show the more colored pixels of excellent specific property.

In addition, by having used the B-2 of the terephthalic acid (TPA) that functional group's number is 2, with to have used functional group's number be 31,2, when the B-1 of 4-benzenetriol compares, in the known B-1 that has used more giving property of the hydrogen compound of functional number, obtained more excellent effect.

On the other hand, in the B of not hydrogeneous giving property compound comparison-1～B compares-6, in above-mentioned arbitrary project, comprise " * ", can't obtain the colored pixels with desired characteristic.

More specifically, as B compares as shown in the of-3, do not have the pyromellitic acid tetramethyl ester of the functional group of regulation even use structure and pyromellitic acid are similar, the form and aspect thermotolerance of the resulting colored pixels of result is also poor.In addition, as B compares as shown in the of-4, even use the benzoic acid with 1 carboxyl, the brightness thermotolerance of the resulting colored pixels of result is also poor.And then, as B compares as shown in the of-5, even use, under 25 ℃, 1 atmospheric pressure, be the BT of liquid, the form and aspect brightness of the resulting colored pixels of result is also poor.

The B relatively scheme shown in-6 is equivalent to the embodiment 31 that former application is particular instantiation in No. 2008-292970, Japanese JP.In this B compares-6, obtained the result of form and aspect luminance differences.In addition, under stricter heat-resisting condition (235 ℃), can't show sufficient thermotolerance.

On the other hand, at B, relatively added in-6 in the composition of the present application of above-mentioned giving property of hydrogen compound, obtained all improved results of the stable on heating projects of form and aspect brightness.

As B compares as shown in the of-7, when the content of giving property of hydrogen compound is less than specialized range, brightness as a result and poor heat resistance.In addition, as B relatively as shown in the of-8, when the content of giving property of hydrogen compound, during more than specialized range, form and aspect, brightness, thermotolerance and chemical proofing are poor as a result.

Claims (11)

1. a solidification compound, it contains and selects the dyestuff shown in free general formula (1-1), at least a kind of dyestuff in the group that dyestuff shown in dye well general formula (1-3) shown in general formula (1-2) forms, polymerizable monomer, organic solvent and giving property of hydrogen compound, described giving property of hydrogen compound at least has 2 and selects free hydroxyl, carboxyl, amide group, functional group in the group that sulfonic group and phosphonate group form, at 25 ℃, under 1 atmospheric pressure, it is solid, and molecular weight is below 3000, in described functional group, independent of one another or the mutual bonding of 2 carboxyls and form anhydride group, independent of one another or the mutual bonding of carboxyl and amide group and form imide,

The content of described giving property of hydrogen compound is 0.1～12 quality %,

General formula (1-1)

In general formula (1-1), R ₁₁～R ₁₆mean independently respectively hydrogen atom or substituting group; R ₁₇mean hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical; Ma means metallic atom or metallic compound; X ₁expression can with the group of Ma bonding, X ₂expression is used for the required group of electric charge with Ma; X ₁and X ₂independent of one another or mutual bonding and form 5 yuan, 6 yuan or 7 rings;

General formula (1-2)

In general formula (1-2), R ₁₂～R ₁₅mean independently respectively hydrogen atom or substituting group; R ₁₇mean hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical; Ma means metallic atom or metallic compound; X ₃mean NR, nitrogen-atoms, oxygen atom or sulphur atom, wherein R means hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl; X ₄mean NRa, oxygen atom or sulphur atom, wherein Ra means hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl; Y ₁mean NRc, nitrogen-atoms or carbon atom, wherein Rc means hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl; Y ₂mean nitrogen-atoms or carbon atom; R ₁₈and R ₁₉mean independently respectively alkyl, alkenyl, aryl, heterocyclic radical, alkoxy, aryloxy group, alkyl amino, arylamino or heterocyclic amino group; R ₁₈with Y ₁independent of one another or mutual bonding and form 5 yuan, 6 yuan or 7 rings; R ₁₉with Y ₂independent of one another or mutual bonding and form 5 yuan, 6 yuan or 7 rings; X ₅expression can with the group of Ma bonding; A means 0,1 or 2;

General formula (1-3)

In general formula (1-3), R ₁₁～R ₁₆mean independently respectively hydrogen atom or substituting group, R ₁₇mean hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical, Ma means metallic atom or metallic compound.

2. solidification compound according to claim 1, wherein, the quality W of described giving property of hydrogen compound ₁quality W with described dyestuff ₂mass ratio W ₂/ W ₁be 0.05～10.

3. solidification compound according to claim 1 and 2, wherein, the molecular weight of described giving property of hydrogen compound is that molecular weight/functional group's number is more than 36 with the ratio of described functional group number.

4. solidification compound according to claim 1 and 2, its viscosity under 25 ℃ is below 30mPas.

5. solidification compound according to claim 1 and 2, its surface tension under 25 ℃ is 20～40mN/m.

6. solidification compound according to claim 1 and 2, wherein, described solidification compound also contains the dyestuff shown in general formula (3),

General formula (3)

In general formula (3), R ¹mean independently respectively hydrogen atom or substituting group, L means respectively aliphatics or aromatic linking group, Z independently ¹expression forms the required non-metallic atom group of 6 rings, 4 Z together with 2 carbon atoms ¹identical or different, M means the metallic atom of 2 hydrogen atoms, divalent, the metal oxide of divalent, the metal hydroxides of divalent or the metal chloride of divalent, m mean independently respectively 1 or 2, n mean independently respectively 0 or 1, p mean independently respectively 1～5 integer; r ¹, r ², r ³and r ⁴mean independently respectively 0 or 1, meet r ¹+ r ²+ r ³+ r ⁴>=1.

7. the manufacture method of a color filter, it possesses following operation:

The recess entitle of the next door by being formed on substrate being divided by ink-jet method requires the operation of describing of the described solidification compound of any one in 1～6; With

The curing process that the described solidification compound that is ejected into recess is heated.

8. the manufacture method of a color filter, it has following operation:

In the recess of dividing in the next door by being formed on substrate, the described solidification compound of any one in coating claim 1～6, be situated between and carried out pattern exposure and developed by mask, thereby form pattern image.

9. a color filter, it is the color filter of manufacturing by the manufacture method of claim 7 or 8 described color filters.

10. a liquid crystal display, it possesses color filter claimed in claim 9.

11. an image display, it possesses color filter claimed in claim 9.

Images