CN102193312A

CN102193312A - Curing composition, colour filter and manufacturing method thereof, liquid crystal display and image display apparatus

Info

Publication number: CN102193312A
Application number: CN2011100258931A
Authority: CN
Inventors: 松下泰明
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2010-01-25
Filing date: 2011-01-24
Publication date: 2011-09-21
Anticipated expiration: 2031-01-24
Also published as: CN102193312B; JP2011148950A; TW201135358A; KR20110087221A

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, LCD, image display

Technical field

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

Background technology

In recent years, along with personal computer, the particularly development of big picture LCD TV, there is the tendency of the increase in demand of LCD (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 LCD of this color filter, by open and close and R, G and the corresponding electrode of B pixel separately, thereby liquid crystal is worked as shutter (shutter), light carries out colour by R, G and B pixel separately and shows.

Carried out various researchs 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 make color filter by colored resist (color resist) method.

About the printing ink of blueness of record in the patent documentation 1, compare with the printing ink of other colors, 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 the aspects such as manufacturing process that are applied to implement under hot conditions more, it requires level to become very high.

On the other hand, present inventors find, when using in the patent documentation 1 concrete disclosed solidification compound, the form and aspect of resulting colored pixels are requiring under the stable on heating high temperature level deterioration easily recently, and are not necessarily satisfactory in the 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 the color filter.On the other hand, concrete disclosed solidification compound utilizes the heat curing processing to carry out solidifying research in the use patent documentation 1, and the absorption spectrum of colored pixels broadens as a result, can't obtain showing the 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 the 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 excellents such as a kind of optical characteristics that obtains by this solidification compound, thermotolerance, chemical proofing and the manufacturing method of color filter with this specific character are provided.

Present inventors further investigate, and found that, have particular functional group's hydrogen donating compounds by use, can make excellent colored pixels such as brightness, form and aspect, thermotolerance, chemical proofing.

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

＜1〉a kind of solidification compound, its contain be selected from by the dyestuff shown in the dyestuff shown in the general formula described later (1-1), the general formula (1-2), and general formula (1-3) shown in the group formed of dyestuff at least a kind of dyestuff, polymerizable monomer, organic solvent and hydrogen donating compounds, described hydrogen donating compounds has 2 functional groups that are selected from the group of being made up of hydroxyl, carboxyl, amide group, sulfonic group and phosphonate group at least, under 25 ℃, 1 atmospheric pressure 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 hydrogen donating compounds is 0.1～12 quality %.

＜2〉according to＜1〉described solidification compound, wherein, the quality (W of above-mentioned hydrogen donating compounds 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 hydrogen donating compounds is more than 36 with the ratio (molecular weight/functional group's number) of above-mentioned functional group number.

＜4〉according to＜1 〉～＜3 in each described solidification compound, its viscosity under 25 ℃ is below the 30mPas.

＜5〉according to＜1 〉～＜4 in each described solidification compound, its surface tension under 25 ℃ is 20～40mN/m.

＜6〉according to＜1 〉～＜5 in each described solidification compound, it also contains the dyestuff shown in the general formula described later (3).

＜7〉a kind of manufacturing method of color filter, it possesses following operation: describe operation, for the recess of dividing by the next door that is formed on the substrate, by ink-jet method give＜1～＜6 in each described solidification compound; With

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

＜8〉a kind of manufacturing method of color filter, it has following operation: in the recess divided by the next door that is formed on substrate coating＜1 〉～＜6 in each described solidification compound, Jie carries out pattern exposure by mask, and develops, thereby forms pattern image.

＜9〉a kind of color filter, it is by＜7〉or＜8〉described manufacturing method of color filter manufacturing obtain.

＜10〉a kind of LCD, 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 the 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 excellents such as a kind of optical characteristics that obtains by this solidification compound, thermotolerance, chemical proofing and the manufacturing method of color filter with this specific character also are provided.

Description of drawings

Fig. 1 is the process flow diagram of manufacturing process in the embodiment of expression manufacturing 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 manufacturing 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 be selected from by the dyestuff shown in the dyestuff shown in the general formula described later (1-1), the general formula (1-2), and general formula (1-3) shown in the group formed of dyestuff at least a kind of dyestuff, polymerizable monomer, organic solvent and hydrogen donating compounds, described hydrogen donating compounds has the functional group of 2 regulations at least, and is solid under 25 ℃, 1 atmospheric pressure.

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 the colored pixels, as its solution, have expected using the hydrogen donating compounds with specified functional groups.

That is, among the present invention, have the hydrogen donating compounds 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 to show the colored pixels that optical characteristics such as desired form and aspect and brightness and thermotolerance, chemical proofing also are improved.

Below, each constituent (dyestuff, polymerizable monomer, organic solvent, hydrogen donating compounds 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 be selected from by the dyestuff shown in the dyestuff shown in the general formula (1-1), the general formula (1-2), and general formula (1-3) shown in the group formed of dyestuff in two pyrroles's methylene based dyes.

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

Below the dyestuff shown in various is described in detail.

Dyestuff shown in the＜general formula (1-1) 〉

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

General formula (1-1)

In the general formula (1-1), R ₁₁～R ₁₆Represent hydrogen atom or substituting group respectively independently.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), (preferred carbon number is 1～48 to alkyl, more preferably carbon number is 1～24 straight chain, the alkyl of side chain or ring-type, methyl for example, 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), (preferred carbon number is 2～48 to alkenyl, more preferably carbon number is 2～18 alkenyl, vinyl for example, allyl, the 3-butene-1-yl), (preferred carbon number is 6～48 to aryl, more preferably carbon number is 6～24 aryl, phenyl for example, naphthyl), (preferred carbon number is 1～32 to heterocyclic radical, more preferably carbon number is 1～18 heterocyclic radical, thiphene ring for example, pyridine ring, furan nucleus, pyrimidine ring, the benzotriazole ring, the pyrazoles ring, imidazole ring, thiazole ring, isothiazole ring oxazole ring, the thiadiazoles ring, triazole ring, 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), (preferred carbon number is 3～38 to silicyl, more preferably carbon number is 3～18 silicyl, trimethyl silyl for example, triethylsilyl, the tributyl silicyl, t-butyldimethylsilyl, uncle's hexyl dimetylsilyl), hydroxyl, cyano group, nitro, carboxyl, (preferred carbon number is 1～48 to alkoxy, more preferably carbon number is 1～24 alkoxy, methoxyl for example, ethoxy, the 1-butoxy, the 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy, cycloalkyloxy (cyclopentyloxy for example, cyclohexyloxy)), (preferred carbon number is 6～48 to aryloxy group, more preferably carbon number is 6～24 aryloxy group, phenoxy group for example, the 1-naphthoxy), (preferred carbon number is 1～32 to heterocyclic oxy group, more preferably carbon number is 1～18 heterocyclic oxy group, 1-phenyltetrazole-5-oxygen base for example, the 2-tetrahydro-pyran oxy), (preferred carbon number is 1～32 to siloxy, more preferably carbon number is 1～18 siloxy, trimethylsiloxy for example, the t-butyldimethylsilyloxy base, the diphenyl methyl siloxy), (preferred carbon number is 2～48 to acyloxy, more preferably carbon number is 2～24 acyloxy, acetoxyl group for example, new pentane acyloxy, benzoyloxy, dodecane acyl-oxygen base), (preferred carbon number is 2～48 to alkoxy carbonyl oxygen base, more preferably carbon number is 2～24 alkoxy carbonyl oxygen base, ethoxy carbonyl oxygen base for example, tert-butoxy carbonyl oxygen base, cycloalkyloxy carbonyl oxygen base, cyclohexyloxy carbonyl oxygen for example), (preferred carbon number is 7～32 to aryloxy group carbonyl oxygen base, more preferably carbon number is 7～24 aryloxy group carbonyl oxygen base, phenoxy group carbonyl oxygen base for example), (preferred carbon number is 1～48 to carbamoyloxy, more preferably carbon number is 1～24 carbamoyloxy, N for example, N-dimethylamino formyloxy, N-butyl carbamoyloxy, N-phenyl amino formyloxy, N-ethyl-N-phenyl amino formyloxy), (preferred carbon number is 1～32 to sulfamoyloxy, more preferably carbon number is 1～24 sulfamoyloxy, N for example, N-diethyl amino sulfonyloxy, N-propyl group sulfamoyloxy), (preferred carbon number is 1～38 to alkylsulfonyloxy, more preferably carbon number is 1～24 alkylsulfonyloxy, for example sulfonyloxy methyl oxygen base, the cetyl sulfonyloxy, the cyclohexyl sulfonyloxy);

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

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

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

R in the 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 the 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 being replaced by the substituting group more than 2, these substituting groups can be the same or different.

R in the general formula (1-1) ₁₇Expression 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 being replaced by the substituting group more than 2, these substituting groups can be the same or different.

In the general formula (1-1) preferably, R ₁₁And R ₁₆Represent 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 respectively independently, R ₁₂And R ₁₅Represent 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 respectively independently, R ₁₃And R ₁₄Represent 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 respectively independently, R ₁₇Expression hydrogen atom, alkyl, aryl or heterocyclic radical.

More preferably, in the above-mentioned general formula (1-1), R ₁₁And R ₁₆Represent 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 respectively independently, R ₁₂And R ₁₅Represent 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 respectively independently, R ₁₃And R ₁₄Represent 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 respectively independently, R ₁₇Expression hydrogen atom or alkyl.

Particularly preferably be, in the general formula (1-1), R ₁₁And R ₁₆Represent 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 respectively independently, R ₁₂And R ₁₅Represent alkyl, aryl, heterocyclic radical, cyano group, acyl group, alkoxy carbonyl, carbamyl, alkyl sulphonyl, aryl sulfonyl or the group that their combinations are obtained respectively independently, R ₁₃And R ₁₄Represent hydrogen atom, alkyl, aryl, heterocyclic radical or the group that their combinations are obtained respectively independently, R ₁₇The expression hydrogen atom.

Ma in the general formula (1-1) represents metallic atom or metallic compound.As metallic atom or metallic compound, get final product so long as can form the metallic atom or the metallic compound of complex compound, comprise the metallic atom of divalent, the metal oxide of divalent, the metal hydroxides of divalent or the metal chloride of divalent.For example except that 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 make viewpoint such as adaptability, be preferably Fe, Zn, Co, V=O or Cu, most preferably be Zn.

X in the general formula (1-1) ₁So long as can get final product with the group (for example hydroxyl, carboxylic acid group, phosphate, sulfonic group or the like) 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 (for example methyl alcohol, ethanol, propyl alcohol), carboxylic acids (for example acetate) etc. and " metal-chelator " [1] the slope mouth force one.

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

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

Dyestuff shown in the＜general formula (1-2) 〉

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

General formula (1-2)

In the general formula (1-2), R ₁₂～R ₁₅Represent hydrogen atom or substituting group respectively independently.R ₁₇Expression hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical.Ma represents metallic atom or metallic compound.X ₃(R represents hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl to expression NR.), nitrogen-atoms, oxygen atom or sulphur atom, X ₄(Ra represents hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl to expression NRa.), oxygen atom or sulphur atom, Y ₁(Rc represents hydrogen atom, alkyl, alkenyl, aryl, heterocyclic radical, acyl group, alkyl sulphonyl or aryl sulfonyl to expression NRc.), nitrogen-atoms or carbon atom, Y ₂Expression nitrogen-atoms or carbon atom.R ₁₈And R ₁₉Represent alkyl, alkenyl, aryl, heterocyclic radical, alkoxy, aryloxy group, alkyl amino, arylamino or heterocyclic amino group respectively independently.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 represents 0,1 or 2.

R in the general formula (1-2) ₁₂～R ₁₅And R ₁₇Respectively with general formula (1-1) in R ₁₂～R ₁₅And R ₁₇Define identical.

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

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

In the 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 being replaced by the substituting group more than 2, these substituting groups can be the same or different.

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

Alkyl shown in R and the 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 the general formula (1-2), Y ₁Expression NRc, nitrogen-atoms or carbon atom, Y ₂Expression nitrogen-atoms or carbon atom.Rc and above-mentioned X ₃R definition identical.

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

In the 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 yuan of rings can list from by above-mentioned R ₁₈And Y ₁And in the ring that forms of carbon atom 1 key become 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 yuan of 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 being replaced by the substituting group more than 2, these substituting groups can be the same or different.

In the 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 represents 0,1 or 2.

As the preferred mode of the compound shown in the 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 the general formula (1-1), X ₃Be NR (R is hydrogen atom, alkyl), nitrogen-atoms or oxygen atom, X ₄Be NRa (Ra is hydrogen atom, alkyl, heterocyclic radical) or oxygen atom, Y ₁Be NRc (Rc is hydrogen atom or alkyl), nitrogen-atoms or carbon atom, Y ₂Be 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 yuan of rings, perhaps R ₁₉With Y ₂Mutual bonding and form 5 yuan or 6 yuan of rings, a represents 0 or 1.

As the preferred mode of the compound shown in the 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 the general formula (1-1), X ₃And X ₄Be oxygen atom, Y ₁Be NH, Y ₂Be 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 yuan of rings, in addition, R ₁₉With Z ₂Mutual bonding and form 5 yuan or 6 yuan of rings, a represents 0 or 1.

Dyestuff shown in the＜general formula (1-3) 〉

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

General formula (1-3)

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

R in the 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 the general formula (1-3) represents metallic atom or metallic compound, and is identical with the metallic atom or the metallic compound definition of explanation in the general formula (1-1), and its preferred range 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, No. the 5th, 433,896, United States Patent (USP), TOHKEMY 2001-240761 number, TOHKEMY 2002-155052 number, No. the 3614586th, Jap.P., Aust.J.Chem, 1965,11,1835-1845, J.H.Boger etc., Heteroatom Chemistry, Vol.1, the method for record is synthesized among the No.5 (1990) etc.

Dyestuff shown in the＜general formula (3) 〉

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

General formula (3)

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

As R ¹Shown " substituting group ", so long as the group that can replace gets final product, (preferred total carbon atom number is 1～15 alkyl, alkenyl, alkynyl for example can to list aliphatic group.For example can list methyl, ethyl, vinyl, allyl, ethinyl, isopropenyl, 2-ethylhexyl etc.), (preferred 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.), (preferred total carbon atom number is 3～15 to heterocyclic radical, and more preferably total carbon atom number is 3～10.For example can list 3-pyridine radicals, 2-pyridine radicals, 2-pyrimidine radicals, 2-pyrazinyl, 1-piperidyl etc.), (preferred total carbon atom number is 1～16, and more preferably total carbon atom number is 1～12 for cyano group, carboxyl, carbamyl.For example can list 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.)、

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

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

(preferred total carbon atom number is 6～16 to aryl sulfonyl, and more preferably total carbon atom number is 6～12.For example can list benzenesulfonyl, 4-tert-butyl benzene sulfonyl, 4-tosyl, 2-tosyl etc.), (preferred 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.), (preferred total carbon atom number is 2～17 to aliphatics sulfonamido formoxyl, and more preferably total carbon atom number is 2～13.For example can list the amino formoxyl of sulfonyloxy methyl, butyl sulfonamido formoxyl, 2-methyl butyl sulfonamido formoxyl etc.), (preferred total carbon atom number is 7～21 to the Arenesulfonyl amino formoxyl, and more preferably total carbon atom number is 7～17.For example can list phenyl sulfonamido formoxyl etc.), (preferred total carbon atom number is 2～17 to aliphatics carbonyl sulfamoyl, and more preferably total carbon atom number is 2～13.For example can list methyl carbonyl sulfamoyl, butyl carbonyl sulfamoyl, 2-ethylhexyl carbonyl sulfamoyl etc.), (preferred total carbon atom number is 7～21 to the aryl carbonyl sulfamoyl, and more preferably total carbon atom number is 7～17.For example can list phenylcarbonyl group sulfamoyl etc.), (preferred total carbon atom number is 1～16 to aliphatics sulphonyl sulfamoyl, and more preferably total carbon atom number is 1～12.For example can list methyl carbonyl sulfamoyl, butyl carbonyl sulfamoyl, 2-ethylhexyl carbonyl sulfamoyl etc.), (preferred total carbon atom number is 6～16 to the arylsulfonyl sulfamoyl, and more preferably total carbon atom number is 6～12.For example can list 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 not have replacement, can be substituted base yet and replace.In addition, " aryl " can be in monocycle and the condensed ring any one, can not have replacement, also can be substituted base and replace.The group of " heterocyclic radical " to be its heterocycle position have in ring heteroatoms (for example nitrogen-atoms, sulphur atom, oxygen atom) can be in saturated rings and the unsaturated ring any one, also can be monocycle and condensed ring, can not have replacement, also can be substituted base and replace.

Work as R ¹Substituting group during for the group that can further replace, can further have 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; aliphatic group more preferably; 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 the general formula (3), L represents aliphatics or aromatic linking group respectively independently.If use these linking groups, then 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 the L, can not have replacement and can have substituting group yet, preferred total carbon atom number is 1～20 aliphatic group, more preferably total carbon atom number is 1～15 aliphatic group.For example can list methylene, ethylidene, propylidene, butylidene etc.

As the aromatic linking group shown in the L, can not have replacement and can have substituting group yet, preferred total carbon atom number is 6～20 aromatic group, more preferably total carbon atom number is 6～16 aromatic group.For example can list phenylene, naphthylene etc., most preferably be phenylene.

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

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

In the general formula (3), M represents 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 are Cu.

In the general formula (3), m represents 1 or 2 respectively independently, and m is preferably 2.

N represents 0 or 1 respectively independently, and n is preferably 1.

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

Among the present invention, a plurality of R in the 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 the 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 with-S (=O) _mUnder the situation of-Direct Bonding, R ₁Be preferably-OY, preferably with-S (=O) _m-constitute together with tetraazatetradecane porphyrin ring Direct Bonding-SO ₃Y (m=2).

Y represents hydrogen atom, metallic atom or conjugate acid.Metallic atom shown in the Y can list Li, Na, K, Mg, Ca, is preferably Li, Na, K.As the alkali that forms the conjugate acid shown in the 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 (for example 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 ⁴Represent 0 or 1 respectively independently, r ¹+ r ²+ r ³+ r ⁴Be more than 1, r ¹+ r ²+ r ³+ r ⁴Be preferably 2～4.In addition, also preferred r 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, be not limited thereto among the present invention.In addition, in following example, preferably can list T-95, T-97, T-114, T-115, T-117, T-127, T-130.

T-84 T-85 T-86 T-87

-SO ₂CH ₃ -SO ₂(CH ₂) ₂OC ₂H ₅ -SO ₂(CH ₂) ₂O(CH ₂) ₂OCH ₃ -SO ₂(CH ₂) ₃CONH(CH ₂) ₃OC ₂H ₅

T-88 T-89 T-90

-SO ₂CH ₂CH ₂CH ₂SO ₃Na -SO ₂(CH ₂) ₃SO ₂N(CH ₂CH ₂CH ₂OCH ₃) ₂

T-91 T-92 T-93 T-94

-SO ₂(CH ₂) ₂O(CH ₂) ₂O(CH ₂) ₂OCH ₃ -SO ₂(CH ₂) ₃COOH -SO ₂(CH ₂) ₃COOCH ₅

T-95 T-96 T-97

-SO ₂(CH ₂) ₃SO ₂NH(CH ₂) ₃OC ₄H ₉ -SO ₂(CH ₂) ₃SO ₂NH(CH ₂) ₃OC ₂H ₅

T-98 T-99

-SO ₂-NHCOCH ₃

T-101 T-102 T-103 T-104 T-105

-SO ₂-CH ₂CH ₂COOC ₂H ₅

T-106 T-107 T-108 T-109 T-110

T-111 T-112 T-113 T-114

T-115 T-116 T-117 T-118

T-120 T-121 T-122 T-123 T-124 T-119

-SO ₂NH ₂ -SO ₂NHC ₂H ₅

-SO ₂NH(CH ₂) ₃OCH ₃ -SO ₂NH(CH ₂) ₂OCH ₃ -SO ₂NH(CH ₂) ₃OC ₂H ₅

T-125 T-126 T-127 T-128 T-129

T-130 T-131 T-134

-SO ₃Na

T-135 T-136 T-137 T-138

T-139 T-140 T-141

The object lesson of the dyestuff shown in the 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

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

CB-7

T-46

T-49

CB-8

T-46

T-56

CB-9

T-89

CB-10

T-89

T-88

CB-11

T-89

T-99

CB-12

T-89

T-141

CB-13

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

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

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

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

CB-41

T-116

T-112

CB-42

T-116

T-134

CB-43

T-116

T-141

CB-44

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 the above-mentioned general formula (3) (tetraazatetradecane porphyrin based dye) can synthesize by the method for for example middle record such as TOHKEMY 2006-58787 communique, TOHKEMY 2006-124379 communique, TOHKEMY 2006-124679 communique.

In the ink for inking, the total content of the dyestuff shown in dyestuff shown in general formula (1-1)～general formula (1-3) and the 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 as the required optical density of color filter, thickness thickening.Therefore black matrix" also needs to thicken, and is difficult to form black matrix", and is therefore not preferred.When content was too much, ink viscosity uprised, and was difficult to ejection, and was difficult for being dissolved in the solvent, and is therefore not preferred.

In addition, in the 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/two pyrroles's methylene based dyes) of the dyestuff (cyanine dye) shown in the general formula (3), the viewpoint that shows the chemical proofing of more excellent outward appearance, excellence 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,, then be not particularly limited as long as satisfy the dissolubility of each composition.

As the object lesson of organic solvent, preferably enumerate water outlet or ester class (for example amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate etc.), ethers (for example diethylene glycol dimethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether etc.), ketone (for example cyclohexanone etc.), aromatic hydrocarbon based (for example dimethylbenzene etc.), alcohols (for example phenmethylol etc.), dicyclohexyl methylamine etc.They can use more than a kind or 2 kinds and use.

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

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

＜polymerizable monomer 〉

Solidification compound of the present invention contains polymerizable monomer.By the interpolation polymerizable monomer, thereby make the adaptation of drop and substrate improve.And, can expect the raising of 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, for example can list cationically polymerizable monomer and free radical polymerization monomer etc.Wherein, aspect many from various substituent variations, that obtain is easily considered, preferably contains free radical polymerization monomers such as (methyl) acrylic monomer.

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

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

Kind as above-mentioned polymerizable group is not particularly limited, and as mentioned above, is preferably acryloxy, methacryloxy especially.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, as (methyl) acrylic monomer is acrylate monomer and methacrylate monomers, can list acrylate such as the acrylate of 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 %, more preferably 40～80 quality % in the solid constituent of solidification compound.If the use amount of polymerizable monomer in above-mentioned scope, then because the polymerization of pixel portions is abundant, therefore is difficult for causing the generation of the damage that the deficiency by the film strength of pixel portions causes.Here, the solid constituent that is used for determining the solidification compound of cooperation ratio comprises the whole compositions except that desolvating, and aqueous polymerizable monomer etc. is also included within the solid constituent.

＜hydrogen donating compounds 〉

Solidification compound of the present invention contains the hydrogen donating compounds with functional group of regulation more than 2.By using this hydrogen donating compounds, 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 the hydrogen donating compounds 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, then can take into account other performances such as form and aspect optimization, thermotolerance optimization effect and chemical proofing, therefore preferred.

The hydrogen donating compounds has 2 at least and is selected from by hydroxyl (OH), carboxyl (COOH), amide group (NHCOR ,-CONHR (R is an organic group)), sulfonic group (SO ₃H), phosphonate group (PO ₃H ₂) functional group in the group formed.In addition, the kind of functional group can be identical, also can be different.In addition, be under the situation of carboxyl 2 functional groups, they can bondings and form the acid anhydride (CO-O-CO-).In addition, carboxyl and amide group also can bondings and are formed imide (CO-NH-CO-).

In the 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 are preferably hydroxyl, carboxyl especially.

In addition, the hydrogen donating compounds has 2 above-mentioned functional groups at least.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,, be preferably more than 3, more preferably 3～8, be preferably 3～6 especially as the number of this functional group from the more excellent aspect of effect.In addition, when functional group outnumber 8 the time, poorly soluble in solvent of dyestuff or dyestuff and hydrogen donating compounds can't obtain the abundant improvement of the characteristic of colored pixels sometimes.

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

The hydrogen donating compounds is a solid under 25 ℃, 1 atmospheric pressure.By this compound under this condition is solid, thereby also shows sufficient thermotolerance in heat curing process etc., and then helps the thermotolerance of the dyestuff in the colored pixels to improve.

More specifically, as the fusing point (T of hydrogen donating compounds _m), be preferably more than 40 ℃, more preferably more than 80 ℃.Be not particularly limited about the upper limit, usually below 230 ℃.In addition, the Measurement of melting point method is not particularly limited, and can measure by differential scanning type calorimeter known method such as (DSC).

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

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

As the optimal way of hydrogen donating compounds, to fasten with the pass of above-mentioned functional group number, 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 preferably 42～133 especially.If in above-mentioned scope, then can improve the form and aspect brightness thermotolerance of resulting colored pixels effectively.

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

General formula (2)

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

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

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, preferred carbon number is 6～18 aromatic hydrocarbyl (being preferably phenyl ring, cyclohexyl biphenyl, naphthalene nucleus).

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 the 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, the more excellent aspect of form and aspect brightness thermotolerance chemical proofing from colored pixels, be preferably-the OH base ,-the COOH base ,-the CONHR base, more preferably-the OH base ,-the COOH base.B can be identical, also can be different.In addition, R represents organic group, and preferred carbon number is 1～4 alkyl, aryl.

In addition, adjacent 2 B also can bonding and form anhydride group (CO-O-OC-) or the carbimide base (CO-NH-CO-).

In the general formula (2), n represents 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 preferably 3～6 especially.

When n is 1, can't obtain effect of sufficient as mentioned above.In addition, when n surpassed 8, poorly soluble in solvent of dyestuff or dyestuff and hydrogen donating compounds can't obtain the abundant improvement of the characteristic of colored pixels sometimes.

In addition, in the solidification compound, the hydrogen donating compounds can only be used a kind, and also two or more kinds may be used.

As the hydrogen donating compounds of using among 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-tartrate diamides etc.

The content of hydrogen donating compounds is 0.1～12 quality % with respect to the solidification compound total amount, and more preferably 0.3～8 quality % is preferably 1～8 quality % especially.By this content is set in the above-mentioned scope, thereby can obtain to show the colored pixels of 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 surpassed 12 quality %, the form and aspect of resulting colored pixels, brightness, thermotolerance and drug resistance were poor.

Quality (the W of the hydrogen donating compounds in the 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, then the form and aspect brightness thermotolerance of resulting colored pixels is more excellent.

Quality (the W of the hydrogen donating compounds in the 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, then the form and aspect brightness thermotolerance of resulting colored pixels is more excellent.

＜surfactant 〉

Can also use surfactant in the 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, the Japanese kokai publication hei 11-133600 communique disclosed surfactant as preferred surfactants.

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

＜polymerization initiator 〉

In order to promote the polyreaction of polymerizable monomer, can use polymerization initiator in the solidification compound of the present invention.Polymerization initiator can be selected according to kind, the polymerization path of free radical polymerization monomer used in the solidification compound, for example can list 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 the solidification compound, more preferably 1～30 quality %.If content in above-mentioned scope, then can form better sensitivity and firm solidified portion.

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, from the more excellent aspect of each characteristic of resulting colored pixels, with respect to total composition, dyestuff shown in dyestuff～general formula (1-3) shown in the 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 the 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 hydrogen donating compounds is preferably 0.1～12 quality %, more preferably 0.3～8 quality %.

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

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 spray, then be not particularly limited by ink gun.Wherein, from the viewpoint of coating and the stability by ink-jet ejection, preferred composition viscosity 25 ℃ down for below the 30mPas, more preferably 2～30mPas, more preferably 2～20mPas.In addition, when in device, spraying, preferably the temperature of solidification compound is remained in 20～80 ℃ the scope roughly under the uniform temperature.If the temperature of device is set at high temperature, then the viscosity of solidification compound reduces, and can spray more full-bodied composition.

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

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

Above-mentioned surface tension is to adopt usually used surface tensiometer (manufacturing of the interface science of for example coordinating Co., Ltd., surface tensiometer FACE SURFACE TENSIOMETER CBVB-A3 etc.) to measure the value that obtains by Wilhelmy (Wilhelmy) method under 25 ℃ of liquid temperature, 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 that uses of solid-state image pickup (for example 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.Be preferably used as ink for inking especially.

＜colored pixels (color image) 〉

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

In the XYZ color specification system, color can be by (Y) these 3 parameters are as shown in the formula expression for x, y.At this moment, following x, y are the parameters of expression 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, is preferably more than 7, more preferably more than 10, is preferably more than 12 especially.

＜color filter and manufacture method thereof 〉

Use the manufacturing method of 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 manufacturing method of color filter of utilizing ink-jet method is elaborated.

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

Fig. 1 is the process flow diagram of manufacturing process in the embodiment of expression manufacturing 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 manufacturing method of color filter of the present invention and the schematic section of color filter.

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 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 to the recess between the adjacent next door 14 16 by ink-jet method; Thereby the diaphragm 22 that is formed for protecting formed colored pixels 20 is made 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 following operation as mentioned above: the recess 16 by 14 of ink-jet method counter septums with the form ejection of drop and give printing ink 18 describe operation S110 (with reference to Fig. 2 (c)); Thereby make printing ink 18 dryings that are endowed recess 16 and remove the pretreatment process S112 (with reference to Fig. 2 (d)) that removal ink 18 interior solvents form the printing ink 18a of the remnants of defeated troops; By making the 18a of printing ink remnants of defeated troops polymerization and solidify, thereby form the curing process S114 (with reference to Fig. 2 (e)) of colored pixels 20 to the irradiation process of the irradiation of the 18a of the printing ink remnants of defeated troops in the recess on the substrate 12 16 active energy ray and/or to the heating process that the 18a of the printing ink remnants of defeated troops heats.

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

＜pixel forms operation 〉

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

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

As employed ink gun, can use the 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 ejection portion (nozzle) of ink gun is not limited to single-row configuration, can be set at the multiple row configuration, also can be set at staggered trellis configuration.

As the color filter that uses ink for inking of the present invention to make, 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, forms by yellow (Y) and cyan (C), the blueness (B) that obtains by solidification compound of the present invention or the color filter etc. of colored pixels of 4～6 kinds of colors that further has the colored pixels of yellow (Y), magenta (M), cyan (C) with the redness (R) that forms by yellow (Y) and magenta (M).

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

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

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

＜curing process 〉

In the manufacturing method of color filter of the present invention, the operation that the uncured pixel printing ink 18a of irradiation by active energy ray or the heat form and aspect that red (R), green (G) and blue (B) etc. are desired solidifies can be set.In addition, in order to implement the irradiation of active energy ray, the device of 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 the colored pixels that shows excellent form and aspect brightness thermotolerance chemical proofing by heat curing, and technologies such as rayed can be set.

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

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

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

In addition, in using the manufacturing method of color filter of ink for inking of the present invention, utilizing thermal treatment to carry out as pretreatment process S112, can being provided with and preheating operation before pixel forms polymerization with the printing ink in the recess (uncured pixel).The heating-up temperature that preheats in the operation is not particularly limited, when the temperature that uncured pixel printing ink is begun thermal polymerization is made as T ℃, be preferably and be lower than temperature T ℃, 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 make color filter effectively, and, because the viscosity of the printing ink remnants of defeated troops reduces because of heat, so can obtain higher flowability, can obtain to have the color filter of the pixel of high flatness.

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

＜next door forms operation 〉

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

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

In addition, next door forms among the operation S102, 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 handle.

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

Shown in Fig. 2 (e), after forming next door 14 and pixel 20 on the substrate 12, making color filter 10, in order to improve permanance, 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 next doors 14 such as R, G, B, and makes and have an even surface.

(colored resist method)

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

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

The exposure light source that can be suitable for is not particularly limited, but is preferably the light source with the following wavelength of 400nm.For example 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. can be utilized, when only using certain wavelengths, also optical filter can be utilized.

Can also utilize 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.

The curing process that by heating and/or exposure it is further solidified as required to formed pattern can also be set.Light or radioactive ray as use this moment especially preferably adopt i line isoradial.

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

As the developer solution that is used for manufacturing method of color filter of the present invention, as long as have want the to develop zone (uncured portion) of removing and the composition that can not dissolve zone (solidified portion) in addition that can dissolve solidification compound of the present invention, then can use any developer solution.Particularly can use the combination of various organic solvents and the aqueous solution of alkalescence.As this organic solvent, the above-mentioned solvent that uses 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, for example can list 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 preferred the use.

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

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.

Color filter of the present invention for example can preferably be applicable to the purposes that image demonstration, the particularly coloured image of portable terminal devices such as LCD, TV, personal computer, liquid crystal projection apparatus, game machine, portable phone, digital camera, auto-navigation system etc. show with being not particularly limited.

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

Embodiment

Below list embodiment the present invention is carried out more specific description.Material shown in the 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, among the following embodiment, unless otherwise specified, " % " reaches " part " expression " quality % " and reaches " mass parts ", and molecular weight is represented weight-average molecular weight.

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

At first, take by weighing K pigment dispersing thing 1, the propylene glycol monomethyl ether of the amount of record in the table 1, stirred 10 minutes in the following mixing of 24 ℃ of temperature (± 2 ℃) and with 150rpm.Stir on one side again, take by weighing MEK, bonding agent 2, Hydroquinone monomethylether, the DPHA liquid, 2 of the amount of record in the 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 under 25 ℃ of temperature (± 2 ℃), add successively, under 40 ℃ of temperature (± 2 ℃), stirred 30 minutes, thereby obtain heavy colour composition K1 with 150rpm.In addition, the amount of record is a mass parts in the table 1, specifically is following composition.

＜K pigment dispersing thing 1 〉

Carbon black (Nipex35 that Degussa company makes) 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

(contain that the polymerization inhibitor MEHQ of 500ppm, Japanese chemical drug corporate system make, 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)

After the washing of alkali-free glass substrate usefulness UV wash mill, wash by brush with washing agent, carry out ultrasonic washing with ultrapure water again.With substrate 120 ℃ of following thermal treatments 3 minutes, thereby make the surface state stabilization.

After the substrate cooling and adjusting the temperature to 23 ℃, (エ Off エ one エスアジア company makes, trade name: MH-1600), coating is the heavy colour composition K1 of modulation as mentioned above with coating machine to utilize the glass substrate with slit-shaped nozzle.Then with 30 seconds of VCD (Minton dryer, Tokyo answer chemical industry company to make) with the partial solvent drying, thereby make the flowability disappearance of coating layer, then 120 ℃ of following 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 (manufacturing of the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd.), under the state that substrate and mask (the quartzy exposed mask with picture pattern) stand vertically, with the distance setting between exposed mask face and the heavy colour composition layer K1 is 200 μ m, under blanket of nitrogen, be 300mJ/cm with the exposure ²According to the next door width is that 20 μ m, interval width are that 100 μ m carry out pattern exposure.

Then, with the spray spout pure water of spraying, behind the surperficial uniformly wet with heavy colour composition layer K1, with KOH is that 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) is that 0.04MPa carries out 80 seconds sprays and develops with flat burner pressure under 23 ℃, obtains the patterning image.Then, by the pressure injection ultrapure water of UHV (ultra-high voltage) Washing spray nozzle with 9.8MPa, carrying out residue and remove, is 2500mJ/cm with the exposure under atmosphere ²Carry out post-exposure from the face side that is formed with heavy colour composition layer K1 of substrate, utilize baking oven 240 ℃ of down heating 50 minutes, 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 oleophobic China inkization Cement Composite Treated by Plasma under the following conditions.

Using gases: CF ₄

Gas flow: 80sccm

Pressure: 40Pa

RF power: 50W

Processing time: 30sec

＜blue (B) is with printing ink and magenta ink 〉

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

It is as follows with the detailed content of each material of printing ink and magenta ink to be used for modulation blue (B).

(organic solvent)

Cyclohexanone (with the pure medicine manufacturing of light)

N-Methyl pyrrolidone (with the pure medicine manufacturing of light)

1,3-BGDA (make: the 1,3 butylene glycol diacetate esters) (monomer) by Daicel chemical industry

DPHA (Japanese chemical drug corporate system is made (KAYARAD DPHA))

: dipentaerythritol acrylate

DPCA-60 (Japanese chemical drug corporate system is made (KAYARAD DPCA-60))

: caprolactone modification dipentaerythritol acrylate

(surfactant)

(シリコ one Application company of SHIN-ETSU HANTOTAI makes KF-353: polyether modified silicon oil)

F781-F (make: Megafac F781F) by big Japanese ink chemical industry

(polymerization initiator)

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

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

(hydrogen donating compounds)

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:(+)-and N, N '-diallyl-L-tartrate 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)

1,2,4-butantriol (3 yuan alcohol, room temperature liquid)

(dyestuff)

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

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

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

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

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

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

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

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

＜utilize the manufacturing of the color filter of ink-jet method 〉

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

Then, by in 220 ℃ baking oven, leaving standstill 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 manufacturing of the color filter of colored resist method 〉

On the above-mentioned substrate that obtains with recess, 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 curable.Then, carry out 120 heat treated in second (prebake conditions) with 100 ℃ hot plate.Then, using i line stepping exposure device FPA-3000i5+ (Canon Co., Ltd. system), is that the island-shaped pattern mask in 180 μ m * 450 μ m four directions is with 2000mJ/cm by pattern under the wavelength of 365nm ²Shine.Then, will be formed with the substrate-placing of coated film in rotary spray formula developing machine (DW-30 type through shining; Chemitronics Co., Ltd. makes) horizontal rotating table on, under 23 ℃, carry out infiltration (puddle, the puddle) development in 60 seconds with MEK, make monochromatic color filter.

＜viscosity, capillary mensuration 〉

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

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

(condition determination)

Use rotor: 1 ° of 34 ' * R24

Minute: 2 minutes

Measure temperature: 25 ℃

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

＜form and aspect 〉

Form and aspect about the monochromatic color filter made by above-mentioned ink-jet method, when light source uses illuminant-C, if in the scope (scope A) of 0.130＜x＜0.140 and 0.090＜y＜0.120 then 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 then be made as zero, if in scope in addition then be made as *.The mensuration of form and aspect is used UV-560 (Japanese beam split company make).Show the result in the following table 4.

＜brightness 〉

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

＜thermotolerance evaluation 〉

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

In addition, Δ Eab utilizes CIE1976 (L*, a*, b*) the spatial table colour system value of being 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 〉

To in the chemicals of estimating (N-Methyl pyrrolidone, ethanol), flood 20 minutes by the monochromatic color filter that above-mentioned ink-jet method is made, measure the form and aspect of its front and back.The mensuration of form and aspect is used UV-560 (Japanese beam split company make), Δ Eab is lower than 3 the ◎ that is made as.Be more than 3 with Δ Eab and be lower than 7 be made as zero, be more than 7 with Δ Eab and be lower than 15 the △ that is made as, with Δ Eab be being made as more than 15 *.Show the result in the 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 (Japanese beam split Co., Ltd. makes, trade name " V-560 ") to measure.According to the absorption spectrum that records, obtain the half breadth of maximum absorption band.With half breadth is that situation below the 45nm is made as ◎, will be made as zero above 45nm and the following situation of 50nm, and the situation that will surpass below 50nm and the 60nm be made as △, will be made as above the situation of 60nm *.Show the result in the table 5.

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

By table 4 and 5 as can be known, use solidification compound of the present invention, optical characteristics excellences such as the form and aspect of the colored pixels that obtains 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 evaluation with same " form and aspect " " brightness " " thermotolerance " " chemical proofing " of the monochromatic color filter of making by ink-jet method.

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

In addition, with used functional group's number be 2 terephthalic acid (TPA) B-2, with used functional group's number be 31,2, when the B-1 of 4-benzenetriol compares, used as can be known among the B-1 of the more hydrogen donating compounds of functional number and obtained more excellent effect.

On the other hand, the B of hydrogeneous donating compounds not relatively-1～B comprise " * " in above-mentioned arbitrary project relatively in-6, can't obtain to have the colored pixels of desired characteristic.

More specifically, compare shown in-3 as B, do not have the pyromellitic acid tetramethyl ester of the functional group of regulation even utilization structure and pyromellitic acid are similar, the form and aspect thermotolerance of the resulting colored pixels of result is also poor.In addition, compare shown in-4 as B, even use the benzoic acid with 1 carboxyl, the brightness thermotolerance of the resulting colored pixels of result is also poor.And then, compare shown in-5 as B, be 1,2 of liquid even use under 25 ℃, 1 atmospheric pressure, the 4-butantriol, 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 a particular instantiation in TOHKEMY 2008-292970 number.Compare in-6 at this B, 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, compare in the composition of the present application that has added above-mentioned hydrogen donating compounds in-6, obtained all improved result of the stable on heating projects of form and aspect brightness at B.

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

Claims

1. solidification compound, it contains the dyestuff that is selected from by shown in the general formula (1-1), at least a kind of dyestuff in the group that dyestuff shown in the dye well general formula (1-3) shown in the general formula (1-2) is formed, polymerizable monomer, organic solvent and hydrogen donating compounds, described hydrogen donating compounds has 2 at least and is selected from by hydroxyl, carboxyl, amide group, functional group in the group that sulfonic group and phosphonate group are formed, at 25 ℃, 1 atmospheric pressure is solid down, and molecular weight is below 3000, in the described functional group, 2 carboxyls can bondings and are formed anhydride group, carboxyl and amide group can bondings and are formed imide

The content of described hydrogen donating compounds is 0.1～12 quality %,

General formula (1-1)

In the general formula (1-1), R ₁₁～R ₁₆Represent hydrogen atom or substituting group respectively independently; R ₁₇Expression hydrogen atom, halogen atom, alkyl, aryl or heterocyclic radical; Ma represents 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 ₂Bonding and form 5 yuan, 6 yuan or 7 yuan of rings mutually;

General formula (1-2)

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

General formula (1-3)

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

2. solidification compound according to claim 1, wherein, the quality W of described hydrogen donating compounds 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 hydrogen donating compounds 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 the 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 the general formula (3),

General formula (3)

In the general formula (3), R ¹Represent hydrogen atom or substituting group respectively independently, L represents aliphatics or aromatic linking group, Z respectively independently ¹Expression forms 6 yuan of non-metallic atom groups that ring is required, 4 Z with 2 carbon atoms ¹Can be the same or different, M represents 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 represents 1 or 2 respectively independently, and n represents 0 or 1 respectively independently, and p represents 1～5 integer respectively independently; r ¹, r ², r ³And r ⁴Represent 0 or 1 respectively independently, satisfy r ¹+ r ²+ r ³+ r ⁴〉=1.

7. manufacturing method of color filter, it possesses following operation:

By the describe operation of ink-jet method to each described solidification compound in the recess entitle requirement 1～6 of dividing by the next door that is formed on the substrate; With

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

8. manufacturing method of color filter, it has following operation:

Each described solidification compound in the coating claim 1～6 in the recess of dividing by the next door that is formed on the substrate is situated between and carries out pattern exposure and development by mask, thereby forms pattern image.

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

10. LCD, it possesses the described color filter of claim 9.

11. an image display, it possesses the described color filter of claim 9.