CN101546121A - Color cured composition, a color filter, a method for manufacturing the color filter and a liquid crystal display device - Google Patents

Abstract

The present invention provides a color cured composition, a color filter, a method for manufacturing the color filter and a liquid crystal display device, the color cured composition may form high-fineness color pattern with conical section shape and excellent film strength by exposing, developing and heating. The color cured composition contains (a) polymeric monomer having two ethylenic linkage type unsaturated linkage in molecule or oligomer, (b) photoinitiator, (c) thermo-crosslinking agent and (d) colorant; the (a) I/O value of the polymeric monomer having two ethylenic linkage type unsaturated linkage in molecule or oligomer is lower than 0.65, distance between unsaturated linkages in molecule is less than 60 atoms, and more than two ring structures are provided in the molecule; and content of the (d) colorant is more than 30 weight% and less than 60 weight% relative total solid component of the color cured composition.

Description

Cured composition for color, color filter and manufacture method thereof and liquid crystal indicator

Technical field

The present invention relates to cured composition for color, have color filter and the manufacture method and the liquid crystal indicator of the colored pattern that uses this cured composition for color and form.

Background technology

In the past, cured composition for color was applied to various purposes.

For example known use contains (for example, with reference to the TOHKEMY 2006-243543 communiques) such as permanent pattern formation methods of the photosensitive composite of bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater, thermal cross-linking agent and colorant.

In addition, except that this purposes, for example, for the pixel (colored pattern) that forms color filter also can be used cured composition for color.

In recent years, color filter has not only to monitor but also purposes enlarges in televisor (TV) trend in liquid crystal display cells (LCD) purposes.Along with the trend that this purposes enlarges, color filter is also required gradually the color characteristics of height at aspects such as colourity, contrasts.In addition, in the color filter of image sensor (solid-state imager) purposes, also similarly require the reduction of misalignment, the high color filter of color characteristics such as raising of color capacity of decomposition gradually, wish that in addition height becomes more meticulous.

As mentioned above, in recent years, the high colorrendering quality of color filter requires to improve, and there is the trend of high pigment levelsization in cured composition for color.But, use the high pigment levels change cured composition for color when forming colored pattern by photoetching process, pigment can hinder or absorb ultraviolet seeing through, and is therefore significantly under-exposed, can't obtain the trend of sufficient deep curable when having exposure.Consequently, take place easily recessedly in developing procedure, forming cross sectional shape is the colored pattern of back taper, has the problem for the adaptation difference of substrate etc.

The technology that suppresses the generation of such concave shape has proposed several in the past.One of them discloses following technology: by add chain-transferring agent in photosensitive composite, form rectangle or positive taper (for example, with reference to TOHKEMY 2002-167404 communique) after development.

In addition, as other motion, following technology being disclosed: has imino group by comprising in photosensitive composite, the multipolymer of epoxy radicals forms positive taper (for example, with reference to TOHKEMY 2004-341245 communique).

But, in above-mentioned two kinds of technology, for example, under pigment concentration is situation more than 30%, develop and heat treated after, be difficult to form high colored pattern meticulous, positive conical in shape.

In addition, disclose the very high composition of use colorant concentration in the TOHKEMY 2006-349895 communique and formed the technology of the dividing wall of quadrangle form or reverse tapered shapes, but do not put down in writing the technology that forms high colored pattern meticulous, positive conical in shape by exposure, development and heat treated.

Summary of the invention

That is, the present invention makes in view of the aforementioned technical background, is problem with the purpose shown in being achieved as follows.

The object of the present invention is to provide can be by exposure, develop and heat treated forms high meticulous and have a cured composition for color of the good colored pattern of the cross sectional shape of positive taper and film strength.

In addition, other purpose of the present invention be to provide possess high meticulous and have the color filter and the manufacture method thereof of the good colored pattern of the cross sectional shape of positive taper and film strength and a liquid crystal display cells that possesses this color filter.

Find that above-mentioned problem can realize by the following method, thereby finish the present invention.

That is, cured composition for color of the present invention contains (a) have the polymerizable monomer of 2 ethylenic unsaturated links or oligomer, (b) Photoepolymerizationinitiater initiater, (c) thermal cross-linking agent and (d) colorant in molecule; Above-mentioned (a) has the polymerizable monomer of 2 ethylenic unsaturated links in molecule or the I/O value of oligomer is below 0.65, and the distance between the intramolecular ethylenic unsaturated link is 60 below the atom, and has the ring structure more than 2 in molecule; And the content of above-mentioned (d) colorant is more than the 30 quality % and below the 60 quality % with respect to the total solid composition of cured composition for color.

In cured composition for color of the present invention, (c) softening point of thermal cross-linking agent is more than-100 ℃ and below 130 ℃.

In addition, consider that preferred (c) thermal cross-linking agent has the ring structure more than 1 in molecule from the viewpoint of film strength.

Consider that from the viewpoint of film strength the heat cross-linking group equivalent of further preferred (c) thermal cross-linking agent is more than 50 and below 1000.

In addition, cured composition for color of the present invention is preferred for forming the colored pattern in the color filter.

Color filter of the present invention has the colored pattern that uses cured composition for color of the present invention to form on substrate.

In addition, manufacturing method of color filter of the present invention comprises following step: on substrate, use cured composition for color of the present invention by be coated with repeatedly, prebake conditions, exposure, development and heat treated form colored pattern arbitrarily.

Liquid crystal indicator of the present invention is equipped with color filter of the present invention

According to the present invention, a kind of cured composition for color can be provided, it is by exposure, development and heat treated, can obtain high meticulous and have the cross sectional shape and a good colored pattern of film strength of rectangle or positive taper.

In addition, according to the present invention, can provide possess high meticulous and have the color filter and the manufacture method thereof of the good colored pattern of the cross sectional shape of rectangle or positive taper and film strength and a liquid crystal display cells that possesses this color filter.

Embodiment

Below, describe the present invention in detail.

＜cured composition for color 〉

Cured composition for color of the present invention contains (a) and have the polymerizable monomer of 2 ethylenic unsaturated links or oligomer, (b) Photoepolymerizationinitiater initiater, (c) thermal cross-linking agent and (d) colorant in molecule; (a) having the polymerizable monomer of 2 ethylenic unsaturated links or the I/O value of oligomer in molecule is below 0.65, and the distance between the intramolecular ethylenic unsaturated link is 60 below the atom, and has the ring structure more than 2 in molecule; And the content of above-mentioned (d) colorant is more than the 30 quality % and below the 60 quality % with respect to the total solid composition of cured composition for color.

Below, this (a)～(d) composition is described.

The polymerizable monomer or the oligomer of 2 ethylenic unsaturated links ((a) in molecule, have)

(a) among the present invention has the polymerizable monomer of 2 ethylenic unsaturated links in molecule or the I/O value of oligomer is below 0.65, and the distance between the intramolecular ethylenic unsaturated link is 60 below the atom, and has the ring structure more than 2 in molecule.Below suitably these compounds being called " specific 2 functional monomers " describes.

The I/O value of specific 2 functional monomers among the present invention is to be essential below 0.65, is preferably below 0.63, more preferably below 0.6.In addition, the lower limit as specific 2 functional monomers' I/O value is 0.4.

The I/O value is in this scope the time, and the development of cured composition for color is good, can make that the shape of colored pattern is good.

It is essential below the atom that distance between the intramolecular ethylenic unsaturated link of specific 2 functional monomers among the present invention is 60, and it is above and 55 below the atom to be preferably 8 atoms, and more preferably 10 atoms are above and 50 below the atom.

If in this scope, then the development of cured composition for color is good, can make that the shape of colored pattern is good.

In addition, in specific 2 functional monomers, as the divalent group that connects intramolecular ethylenic unsaturated link, can enumerate the divalent linking group that bisphenol-A, Bisphenol F, bisphenol-ap, bisphenol-c, bis-phenol E, bisphenol S, bisphenol Z, dihydroxybiphenyl class, dihydroxy naphthlene class etc. comprise the skeleton with the ring structure more than 2, the linking group of this divalent also can be not have the group that the divalent linking group of ring structure combines with alkylidene, ethyleneoxy, propenyloxy group etc.

The concrete example of specific 2 functional monomers among the present invention (exemplary compounds A-1～A-6) as follows, but the present invention is not limited thereto.

Among the present invention, specific 2 functional monomers can be used alone, and also can be used in combination.

As the content of specific 2 functional monomers in cured composition for color, total solid composition with respect to said composition, be preferably 1.0 quality %～40.0 quality %, more preferably 1.5 quality %～35.0 quality %, more preferably 2.0 quality %～30.0 quality %.Specific 2 functional monomers' content is in above-mentioned scope the time, and curing reaction carries out fully, and the thermal deformation during heat treated simultaneously generates easily and fully, can access the colored pattern with desirable cross sectional shape.

((b) Photoepolymerizationinitiater initiater)

Cured composition for color of the present invention contains (b) Photoepolymerizationinitiater initiater.

As the Photoepolymerizationinitiater initiater that uses in the cured composition for color of the present invention, so long as can decompose and produce initiating accident sequence, just there be particular determination by light-struck energy, can preferably list known Photoepolymerizationinitiater initiater etc.

As Photoepolymerizationinitiater initiater, for example can list, the Lu that puts down in writing in Japanese kokai publication hei 57-6096 communique is for the Jia oxadiazole, at the public clear 59-1281 communique of spy, the spy opens the middle halogenated methyl s-triazine isoreactivity halogen compounds of putting down in writing such as clear 53-133428 communique, at United States Patent (USP) the 4318791st, the ketal of putting down in writing in each instructions such as European patent 88050A, acetal, or aromatic carbonyl such as benzoin alkylether, the aromatic ketone compounds of in No. 4199420 instructions of United States Patent (USP), putting down in writing such as benzophenone, thioxanthene (xanthene) ketone system or the acridine based compound put down in writing in No. 2456741 instructions of French Patent (FRP), open the coumarin series of putting down in writing in the flat 10-62986 communique or comprise the bisglyoxaline based compound of lophine dipolymer class the spy, open organic boron complexes of sulfonium in flat 8-015521 communique etc. etc. the spy.

As Photoepolymerizationinitiater initiater; preferably (1) acetophenone system, (2) ketal system, (3) benzophenone series, (4) benzoin system, benzoyl base system, (5) xanthone system, (6) active halogen compound ((6-1) triazine system, (6-2) halogen are for first oxadiazole system, (6-3) Coumarins system), Photoepolymerizationinitiater initiaters such as (7) acridine system, (8) bisglyoxaline system, (9) oxime ester system.

As (1) acetophenone is Photoepolymerizationinitiater initiater, can for example preferably enumerate, 2,2-diethoxy acetophenone, to dimethylamino acetophenone, 2-hydroxyl-2-methyl-1-phenyl-propane-1-ketone, 4 '-isopropyl-2-hydroxyl-2-methyl-propiophenone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-methyl-1-[4-(methyl mercapto) phenyl]-2-morpholinyl acetone-1 etc.

As (2) ketal is Photoepolymerizationinitiater initiater, can for example preferably list benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetal etc.

As (3) benzophenone series Photoepolymerizationinitiater initiater, can for example preferably list, benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4,4 '-dichloro benzophenone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl acetone-1 etc.

As (4) benzoin system or benzoyl base system Photoepolymerizationinitiater initiater, can for example preferably list benzoin iso-propylether, benzoin isobutyl ether, benzoin methylether, methyl o-benzoyl yl benzoic acid ester etc.

As (5) xanthone is Photoepolymerizationinitiater initiater, can for example preferably list diethyl thioxanthone, diisopropyl thioxanthones, single isopropyl thioxanthone, clopenthixal ketone etc.

(6-1) triazine as (6) active halogen compound is a Photoepolymerizationinitiater initiater, can for example preferably list, 2,4-two (trichloromethyl)-6-p-methoxyphenyl s-triazine, 2,4-two (trichloromethyl)-6-to the methoxyl-styrene s-triazine, 2,4-two (trichloromethyl)-6-(1-to dimethylamino phenyl)-1,3-butadienyl s-triazine, 2,4-two (trichloromethyl)-6-xenyl s-triazine, 2,4-two (trichloromethyl)-6-(to methyl biphenyl) s-triazine, to hydroxyl-oxethyl styryl-2,6-two (trichloromethyl) s-triazine, methoxyl-styrene-2,6-two (trichloromethyl s-triazine), 3,4-dimethoxy-styryl-2,6-two (trichloromethyl) s-triazine, 4-benzo tetrahydrofuran-2,6-two (trichloromethyl) s-triazine, 4-(adjacent bromine is right-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl) s-triazine, 4-(right-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl) s-triazine etc.

Is Photoepolymerizationinitiater initiater as (6-2) Lu for the Jia oxadiazole, can for example preferably list, 2-trichloromethyl-5-styryl-1,3,4 — oxadiazoles, 2-trichloromethyl-5-(cyano styrene base)-1,3,4 — oxadiazoles, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4 — oxadiazoles, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4 — oxadiazoles etc.

As (6-3) Coumarins is Photoepolymerizationinitiater initiater, can for example preferably list 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-chlorine-5-lignocaine ((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin etc.

As (7) acridine is Photoepolymerizationinitiater initiater, can for example preferably list 9-phenylacridine, 1,7-two (9-acridinyl) heptane etc.

As (8) bisglyoxaline is Photoepolymerizationinitiater initiater, can preferably list for example known as the lophine dipolymer, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole base dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole base dipolymer, 2-(2,4-Dimethoxyphenyl)-and 4,5-diphenyl-imidazole base dipolymer or 2-mercaptobenzimidazole, 2,2 '-benzothiazole based bisulfide etc.

Except above-mentioned; can also list 1-phenyl-1; 2-propanedione-2-(adjacent ethoxy carbonyl) oxime, o-benzoyl base-4 '-(benzo sulfydryl) benzoyl-hexyl ketoxime, 2; 4,6-trimethylphenyl carbonyl-diphenyl phosphine oxide, hexafluoro phosphoryl trialkyl Ben Ji phosphonium salt etc.

In the present invention, be not limited to above Photoepolymerizationinitiater initiater, can also use other known Photoepolymerizationinitiater initiater.For example can list, at United States Patent (USP) the 2nd, 367, poly-Ketol aldose (vicinal polyketoaldonyl) compound of the vicinal of putting down in writing in No. 660 instructionss, at United States Patent (USP) the 2nd, 367, No. 661 and the 2nd, 367, α-carbonyls of putting down in writing in No. 670 instructionss, at United States Patent (USP) the 2nd, 448, the acyloin ether of putting down in writing in No. 828 instructionss, at United States Patent (USP) the 2nd, 722, the aromatic series acyloin compound of putting down in writing in No. 512 instructionss that is replaced by α-alkyl, at United States Patent (USP) the 3rd, 046, No. 127 and the 2nd, 951, the multinuclear naphtoquinone compounds of putting down in writing in No. 758 instructionss, at United States Patent (USP) the 3rd, the combination of triarylimidazoles dimer/p-aminophenyl ketone of putting down in writing in 549, No. 367 instructionss, benzothiazole based compound/trihalomethyl group s-triazine based compound of in special public clear 51-No. 48516 communiques, putting down in writing, at J.C.S.Perkin II (1979) 1653-1660, J.C.S.PerkinII (1979) 156-162, Journal ofPhotopolymer Science and Technology (1995) 202-232, the spy opens oxime ester compound of putting down in writing in 2000-No. 66385 communiques etc.

In addition, can also and use these Photoepolymerizationinitiater initiaters.

As the content of (b) Photoepolymerizationinitiater initiater in cured composition for color, with respect to the total solid composition of said composition, be preferably 0.1～15.0 quality %, more preferably 0.5～12.0 quality %, more preferably 1.0～10.0 quality %.The content of Photoepolymerizationinitiater initiater is in above-mentioned scope the time, and polyreaction is carried out well, can form the good film of intensity.

((c) thermal cross-linking agent)

Cured composition for color of the present invention contains (c) thermal cross-linking agent.

By containing this (c) thermal cross-linking agent, utilize the heat treated after exposing, developing, can improve Thermocurable, and the intensity of epithelium is improved.

Here,, consider, be preferably the compound that has the ring structure more than 1 in the molecule from the aspect of pattern formation property, pattern hardness as the thermal cross-linking agent among the present invention.As this ring structure, can list benzene, furans, thiophene, pyrroles, imidazoles, cyclobutane, cyclopentene, cyclohexene, cycloheptene etc.

In addition, the aspect that forms property, pattern hardness from pattern considers, these ring structures preferably at molecular memory at 1～50, more preferably have 1～100.

In addition, as the heat cross-linking group in the thermal cross-linking agent, can enumerate diglycidyl (epoxy) base, oxetanyl (oxetanyl), isocyanate group, allyl etc.

Consider that from the aspect of cross sectional shape, pattern hardness it is more than 50 and 1000 following compounds that these heat cross-linking groups are preferably heat cross-linking group equivalent.More preferably heat cross-linking group equivalent is 80～900, more preferably 100～800 scope.

As thermal cross-linking agent, preferably use epoxy compound.

This epoxy compound is bisphenol A-type, linear phenol-aldehyde resin type, cresols linear phenol-aldehyde resin type, naphthalene type, dicyclopentadiene type, biphenyl type, fluorenes type, ester ring type epoxy type etc. have 2 above epoxide rings in molecule a compound.

Particularly, for example, as bisphenol A-type, decapacitation is enumerated outside EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above change into manufacturing for Dongdu), DENACOL EX-1101, EX-1102, EX-1103 etc. (above change into manufacturing for Nagase), PLACCEL GL-61, GL-62, G101, the G102 (above make for Daicel chemistry), can also enumerate and they similar Bisphenol F types, bisphenol S type.In addition, also can use epoxy acrylate such as Ebecryl 3700,3701,600 (above make for Daicel UCB).

As the linear phenol-aldehyde resin type, can enumerate EPICLON N-740, N-770, N-775, N-885 (above is big Japanese ink chemistry system) etc.

As cresols linear phenol-aldehyde resin type, can enumerate EPICLON N-660, N-665, N-670, N-680, N-695 (above be big Japanese ink chemical industry system), EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above be Dongdu system of changing into), DENACOL EM-125 etc. (above be the Nagase system of changing into); As the naphthalene type, can enumerate EPICLON HP-4032, HP-4032D, HXA-4700 (above is big Japanese ink chemical industry system) etc.; As dicyclopentadiene type, can enumerate HP-7200L, HP-7200, HP-7200H (above is big Japanese ink chemical industry system).

As biphenyl type, can enumerate 3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl etc., as the fluorenes type, can enumerate オ グ ソ-Le PG100, EG100 (above is Osaka Gas Chemical system) etc., as the alicyclic epoxy compound, can enumerate セ ロ キ サ イ De 2021,2081,2083,2085, エ Port リ-De GT-301, GT-302, GT-401, GT-403, EHPE3150 (above be Daicel chemistry system), サ Application ト-ト ST-3000, ST-4000, ST-5080, ST-5100 etc. (above be Dongdu system of changing into) etc.In addition, also can use 1,1,2,2-four (to the glycidoxypropyl phenyl) ethane, three (to the glycidoxypropyl phenyl) methane, triglycidyl group three (hydroxyethyl) isocyanuric acid ester, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, also have as EPOTOHTO YH-434, the YH-434L of amine type epoxy resin, in the skeleton of bisphenol A type epoxy resin with dimer acid modified ethylene oxidic ester etc.

Wherein, consider from the easiness of thermal deformation and the viewpoint of Thermocurable, preferred use softening point is more than-100 ℃ and the compound below 130 ℃, more preferably using softening point is 0 ℃～120 ℃ compound, the further preferred softening point that uses is 20 ℃～110 ℃ a compound, and especially preferably using softening point is 40 ℃～100 ℃ compound.

Particularly, in above-claimed cpd, the structure of preferred linear phenol-aldehyde resin type, cresols linear phenol-aldehyde resin type, naphthalene type, ester ring type epoxy type, more preferably cresols linear phenol-aldehyde resin type, ester ring type epoxy type.

In addition, above-mentioned softening point can be measured by TMA (Rigaku system).

(c) content of thermal cross-linking agent in cured composition for color with respect to the total solid composition of said composition, is preferably 0.1 quality %～20 quality %, more preferably 0.5 quality %～15 quality %, more preferably 1 quality %～10 quality %.The content of thermal cross-linking agent can not damage photo-curable in above-mentioned scope the time, can improve Thermocurable.

((d) colorant)

Cured composition for color of the present invention contains (d) colorant.

There is no particular limitation for colorant contained in the cured composition for color of the present invention, in known various dyestuff or the pigment in the past one or more can be mixed and use.As this colorant,, be preferably pigment from sunproof viewpoint.

-pigment-

As the pigment that can be used for cured composition for color of the present invention, can suitably select to use known in the past various inorganic pigments or organic pigment.As the particle size of pigment, consider that the color filter of suitable use cured composition for color of the present invention is preferably aspects such as high-transmission rate, organic pigment is preferred, and the preferred as far as possible little pigment of particle size that uses.When considering the operability of cured composition for color of the present invention, the average primary particle diameter of preferred pigments is below the 100nm, more preferably below the 30nm, most preferably is 5nm～25nm.Particle diameter is in above-mentioned scope the time, for form the transmissivity height, color characteristics is good and color filter that contrast is high is effective.Average primary particle diameter is tried to achieve according to as described below: observe with SEM or TEM, at 100 particle sizes of the UA part instrumentation of particle, and calculate mean value.

As above-mentioned inorganic pigment, can enumerate metallic compound by expressions such as metal oxide, metallic complex salts.Particularly, can enumerate the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the composite oxides of above-mentioned metal.

As above-mentioned organic pigment, for example can enumerate:

C.I. paratonere 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279

C.I. pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214

C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73,

C.I. pigment Green 7,10,36,37,

C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,79 Cl substituting group is changed to the pigment, 80 of OH,

C.I. pigment violet 1,19,23,27,32,37,42,

C.I. pigment brown 25,28,

C.I. pigment black 1,7 etc.

In the above-mentioned pigment,, can enumerate following pigment as the pigment that can preferably use.But be not limited to these pigment among the present invention.

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,

C.I. pigment orange 36,71,

C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264,

C.I. pigment violet 19,23,32,

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66,

C.I. pigment Green 7,36,37,

C.I. pigment black 1,7.

These organic pigments can use separately, perhaps also can multiplely be used in combination in order to improve excitation.The concrete example of combinations thereof as shown below.

For example, as red pigment, can can be that yellow uitramarine, isoindoline are that yellow uitramarine, quinophthalone are that yellow uitramarine mixes use with bisdiazo also with anthraquione pigmentss, perylene pigment and use or the mixing use separately of diketopyrrolopyrrolecocrystals series pigments with at least a kind in the above-mentioned pigment.For example, as anthraquione pigmentss, can enumerate C.I. paratonere 177, Zuo is a perylene pigment, can enumerate C.I. paratonere 155, C.I. paratonere 224, as the diketopyrrolopyrrolecocrystals series pigments, can enumerate C.I. paratonere 254.Consider that from the viewpoint of colorrendering quality preferred red pigment is mixed with C.I. pigment yellow 83, C.I. pigment yellow 13 9 or C.I. paratonere 177.

In addition, consider that from the viewpoint of transmittance and excitation, colour developing power the mass ratio of red pigment and other pigment is preferably 100:5～100:80.Particularly as mass ratio, scope the best of 100:10～100:65.In addition, with between the red pigment during combination with one another, can contrast colourity and regulate.

In addition, as viridine green, can use the halo phthualocyanine pigment separately, but also can be that yellow uitramarine, quinophthalone are that yellow uitramarine, azomethine are that yellow uitramarine or isoindoline are that yellow uitramarine mixes and uses this halo phthualocyanine pigment and bisdiazo.For example, as above-mentioned example, preferred C.I. pigment Green 7,36,37 with the mixing of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.

Consider that from the viewpoint of transmittance and excitation, NTSC target form and aspect the mass ratio of viridine green and yellow uitramarine is preferably 100:5～100:200.In addition, as above-mentioned mass ratio, be preferably the scope of 100:20～100:150 especially.

As blue pigment, can use phthualocyanine pigment separately, but also can be that violet pigment mixes and uses phthualocyanine pigment Yu dioxazine.As more preferred example, can enumerate the C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.

The mass ratio of blue pigment and violet pigment is preferably 100:0～100:100, more preferably below the 100:70.

In addition, as the pigment that is fit to the black matrix" purposes, can carbon black, graphite, titanium is black, iron oxide, titanium dioxide uses separately or mix use, the combination that preferred carbon black and titanium are deceived.

In addition, consider that from the viewpoint of dispersion stabilization the mass ratio that carbon black and titanium are black is preferably the scope of 100:0～100:60.

Among the present invention, as required, also can use the pigment that above-mentioned organic pigment is carried out miniaturization and whole granulation and obtain.

In the miniaturization of this organic pigment, the preferred method that comprises the operation of pigment being made full-bodied liquid composition with water-miscible organic solvent and water-soluble inorganic salt and grinding of using.

Among the present invention, in the miniaturization of organic pigment, more preferably use following method.

Promptly, this method is: at first, potpourri (liquid composition) to organic pigment, water-miscible organic solvent and water-soluble inorganic salt uses two roller mills, three-roll mill, bowl mill, cylinder grinding machine, dispersion machine, kneader, is total to mixing rolls such as kneader, homogenizer (homogenizer), mixer, single screw rod or double screw extrusion machine, by applying strong shear strength, organic pigment in the potpourri is ground, then this potpourri is put in the water, made pulpous state by stirring machine etc.; Then,, remove water-miscible organic solvent and water-soluble inorganic salt with this dope filtration, washing, dry then, thus obtain the organic pigment of miniaturization.

As the water-miscible organic solvent of the miniaturization operation that is used for pigment, can enumerate methyl alcohol, ethanol, isopropyl alcohol, n-propanol, isobutyl alcohol, normal butyl alcohol, ethylene glycol, diglycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol methyl ether acetate etc.

In addition, as long as be adsorbed on the pigment by using on a small quantity, thereby be not lost in the waste water, just can use benzene,toluene,xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, MEK, methyl isobutyl ketone, cyclohexanone, dimethyl formamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone etc.In addition, can mix as required also that solvent uses more than 2 kinds.

The use amount of these water-miscible organic solvents is the scope of 50 quality %～300 quality % with respect to organic pigment, is preferably the scope of 100 quality %～200 quality %.

In addition, as water-soluble inorganic salt, can use sodium chloride, potassium chloride, lime chloride, barium chloride, sodium sulphate etc. among the present invention.

The use amount of water-soluble inorganic salt is preferably 1 times of quality～50 times quality of organic pigment, though the many persons of use amount have the effect of grinding, considers that from the viewpoint of throughput rate preferred amount is 1 times of quality～10 times quality.

In addition, in order to prevent the dissolving of water-soluble inorganic salt, the moisture in the liquid composition that grinds is preferably below the 1 quality %.

Among the present invention, when the liquid composition that contains organic pigment, water-miscible organic solvent and water-soluble inorganic salt is ground, as long as use above-mentioned case of wet attrition devices such as mixing roll.Operating condition to this case of wet attrition device does not have particular determination, but in order to grind effectively by crushing medium (water-soluble inorganic salt), at device for the operating condition in the situation of kneader be: the blade rotational speed in the device is preferably 10～200rpm, in addition, the speed ratio of two screw rods is big relatively, grind effective, so preferred.In addition, the duration of runs and dry type pulverizing time add up to be preferably 1 hour～8 hours, the internal temperature of device is preferably 50～150 ℃.In addition, as the water-soluble inorganic salt of crushing medium, preferred grinding particle size is that 5 μ m～50 μ m, size distribution are sharp-pointed and for spherical.

By the warm water of above-mentioned potpourri after grinding like that with 80 ℃ is mixed, make the dissolving of water-miscible organic solvent and water-soluble inorganic salt, filter then, wash, and dry dry in baking oven, thus fine organic pigment can be obtained.

In addition, with above-mentioned organic pigment miniaturization the time, by in liquid composition and with at least a portion soluble resin in water-miscible organic solvent, thereby can obtain the few processed pigment of cohesion of the fine and surface pigment when resin-coated, dry.

In the cured composition for color of the present invention, also can use this processed pigment.

Here, as when obtaining processed pigment, use, at least a portion soluble resin in water-miscible organic solvent, can use the known resin that is used as pigment dispersing agent.

-dyestuff-

Among the present invention,, can in composition, dissolve and obtain solidification compound equably using under the situation of dyestuff as colorant.

As not having particular determination, can use in the past as the color filter purposes and known dyestuff as the dyestuff of colorant contained in the cured composition for color of the present invention.For example can enumerate 64-No. 90403 communiques of Japanese kokai publication sho, the spy opens clear 64-No. 91102 communiques, 1-No. 94301 communiques of Te Kaiping, 6-No. 11614 communiques of Te Kaiping, the spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 instructionss, United States Patent (USP) the 5th, 667, No. 920 instructionss, United States Patent (USP) the 5th, 059, No. 500 instructions, 5-No. 333207 communiques of Te Kaiping, 6-No. 35183 communiques of Te Kaiping, 6-No. 51115 communiques of Te Kaiping, 6-No. 194828 communiques of Te Kaiping, 8-No. 211599 communiques of Te Kaiping, 4-No. 249549 communiques of Te Kaiping, 10-No. 123316 communiques of Te Kaiping, 11-No. 302283 communiques of Te Kaiping, 7-No. 286107 communiques of Te Kaiping, the spy opens communique 2001-No. 4823,8-No. 15522 communiques of Te Kaiping, 8-No. 29771 communiques of Te Kaiping, 8-No. 146215 communiques of Te Kaiping, 11-No. 343437 communiques of Te Kaiping, 8-No. 62416 communiques of Te Kaiping, the spy opens communique 2002-No. 14220, the spy opens communique 2002-No. 14221, the spy opens communique 2002-No. 14222, the spy opens communique 2002-No. 14223,8-No. 302224 communiques of Te Kaiping, 8-No. 73758 communiques of Te Kaiping, 8-No. 179120 communiques of Te Kaiping, disclosed pigment in 8-No. 151531 communiques of Te Kaiping etc.

As chemical constitution, can use dyestuffs such as pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, Anthrapyridone system, benzal base system, oxonols (oxonol) are, pyrazolo triazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system etc.

In addition, under the situation of the resist system that carries out the development of water or alkali, according to removing the deluster binder polymer of not irradiation portion and/or the viewpoint of dyestuff fully by developing to come, the situation of acid dyes and/or its derivant can be suitably used in existence.

In addition, also can usefully use direct dyes, basic-dyeable fibre, mordant dye, acid mordant dye, azo dyes, disperse dyes, oil-soluble dyes, food dye and/or their derivant etc.

Acid dyes is so long as have sulfonic acid or the material of the acidic-group of carboxylic acid etc. gets final product, there is no particular limitation, but, can consider to organic solvent or developer solution dissolubility, form property, absorbance, select with the salt of alkali compounds with all necessary performance of the interaction, photostability, thermotolerance etc. of other composition in the composition.

Enumerate the concrete example of acid dyes below, but be not limited to these.

For example can enumerate the purple N of acid alizarine; Acid black 1,2,24,48; Blue VRS, 7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120,129,138,147,158,171,182,192,243,324:1; Acid chrome violet K; Acid fuchsin; Acid green 1,3,5,9,16,25,27,50; Acid orange 6,7,8,10,12,50,51,52,56,63,74,95; Azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274; Acid violet 6B, 7,9,17,19; Indian yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243; Food Huang 3; And the derivant of these dyestuffs.

Wherein as acid dyes, preferred acidic deceives 24; Acid blue 23,25,29,62,80,86,87,92,138,158,182,243,324:1; Acid orange 8,51,56,63,74; Azogeramine, 4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; Acid violet 7; Indian yellow 17,25,29,34,42,72,76,99,111,112,114,116,184,243; The derivant of dyestuffs such as ACID GREEN 25 and these dyestuffs.

In addition, the acid dyes that also preferred above-mentioned azo system, xanthene system, phthalocyanine in addition is also preferably uses C.I. solvent blue 44,38; C.I. the solvent orange 45; The derivant of acid dyess such as rhodamine B, rhodamine 110 and these dyestuffs.

Wherein, as colorant, be preferably the colorant that is selected from triallyl methane series, anthraquinone system, azomethine system, benzal base system, oxonols system, cyanine system, phenothiazine system, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system, pyrazoles azo system, pyridone azo system, the Anthrapyridone system.

The colorant that can use in the present invention is preferably dyestuff or satisfies mean grain size r (unit is nm) is 5≤r≤250, be preferably 10≤r≤200, be preferably the pigment of 15≤r≤150 especially.By using the pigment of such mean grain size r, can obtain having the high-contrast ratio and have the colored pixels of high transmission rate.Here so-called " mean grain size " is meant the mean grain size of the offspring that primary particle (single crystallite) set of pigment forms.

In addition, the size distribution of the offspring of the pigment that can use in the present invention (below, abbreviate " size distribution " as) preferably: the offspring that falls into (mean grain size ± 100) nm is more than the overall 70 quality %, more preferably more than the 80 quality %.

Pigment with above-mentioned mean grain size and size distribution, can by with commercially available pigment with other pigment that according to circumstances uses (usually mean grain size surpass 300nm), preferably make the pigment mixed liquor that obtains with spreading agent and solvent, use for example comminutor such as ball mill, roller mill then, mix dispersion while pulverizing, obtain thereby can modulate.The pigment that obtains like this is the form of dispersible pigment dispersion normally.

-dispersible pigment dispersion-

The dispersible pigment dispersion that contains above-mentioned pigment is that the pigment as (d) colorant is disperseed to form in solvent with spreading agent, pigment derivative.

As spreading agent used herein, use in order to improve dispersing of pigments, for example, can select suitable known pigment dispersing agent or surfactant.

As spreading agent, specifically, can use multiple compound, can enumerate for example organic siloxane polymer KP341 (Shin-Etsu Chemial Co., Ltd's system), (methyl) acrylic acid series (being total to) polymer P OLYFLOW No.75, No.90, the kation of No.95 (chemical industry Co., Ltd. of common prosperity society system), W001 (Yu Business Co., Ltd's system) etc. is a surfactant; Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty ester are surfactant; W004, W005, W017 negative ion such as (Yu Business Co., Ltd's systems) are surfactant; The macromolecule dispersing agent of EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (more than be Ciba SpecialtyChemicals corporate system), デ イ ス パ-ス エ イ De 6, デ イ ス パ-ス エ イ De 8, デ イ ス パ-ス エ イ De 15, デ イ ス パ-ス エ イ De 9100 (being San nopco corporate system) etc.; Various SOLSPERSE spreading agents such as SOLSPERSE 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (Japanese Lubrizol Co., Ltd. system); ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification Co., Ltd. system) and IONET S-20 (Sanyo Chemical Industries, Ltd.'s system), Disperbyk 101,103,106,108,109,111,112,116,130,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (PVC Star Network ケ ミ-Co., Ltd.'s system).In addition, can also list acrylic acid series copolymer etc. has polar group at molecular end or side chain oligomer or polymkeric substance.

As the content of spreading agent in dispersible pigment dispersion, with respect to the quality of above-mentioned pigment, be preferably 1 quality %～100 quality %, more preferably 3 quality %～70 quality %.

In addition, the dispersible pigment dispersion among the present invention can add pigment derivative as required.

In the present invention, there are the part of compatibility or the pigment derivative of polar group to be adsorbed on the surface of pigments by having imported with spreading agent, its adsorption site as spreading agent is used, pigment is dispersed in the dispersible pigment dispersion as fine particle, can prevent that in addition it from condensing once more.That is, come surface of pigments is carried out modification, can effectively promote the absorption of spreading agent by using pigment derivative.

As the pigment derivative of using among the present invention, be precursor skeleton with the organic pigment specifically, imported acidic groups or basic group, aromatic series base on the side chain as substituent compound.Organic pigment as precursor skeleton, specifically can list quinacridone pigment, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindolinone pigment, quinoline series pigments, diketopyrrolo-pyrrole pigment, Benzimidazolinone pigment etc.The general flaxen aromatic series polycyclic compunds such as the naphthalene system that is not called as pigment, anthraquinone system, triazine system, quinoline system that also comprise.

As pigment derivative, can use and open flat 11-49974 communique, spy the spy and open flat 11-189732 communique, spy and open flat 10-245501 communique, spy and open 2006-265528 communique, spy and open flat 8-295810 communique, spy and open flat 11-199796 communique, spy and open 2005-234478 communique, spy and open the pigment derivative that 2003-240938 communique, spy are opened record in the 2001-356210 communique etc.

As pigment derivative involved in the present invention content in dispersible pigment dispersion, with respect to the quality of pigment, be preferably 1～30 quality %, more preferably 3～20 quality %.If this content is in above-mentioned scope the time, can suppress viscosity on one side, make it lower, Yi Bian disperse well, can improve simultaneously the dispersion stabilization after disperseing, can constitute the transmissivity height, can obtain the color characteristics of excellence, when the making color filter, have the high-contrast of good color characteristic.

As the solvent that constitutes dispersible pigment dispersion of the present invention, can list and the same solvent of (f) described later solvent.

Pigment concentration in the dispersible pigment dispersion is preferably 30～90 quality %, more preferably 40～80 quality %.

Dispersible pigment dispersion among the present invention can be modulated by the mixing dispersion step of using various mixers, dispersion machine mixing dispersion.

In addition, mix that dispersion step preferably includes mixing dispersion and loose and handle, but also can omit mixing dispersion at the differential that carries out continuously thereafter.

Specifically, for example, in advance with pigment with the dispersant of adding as required, and then disperse in advance with homogenizer etc., then the dispersion liquid utilization that obtains is used the bead dispersion machine (for example dispersion machine of GETZMANN corporate system (DISPERMAT)) etc. of zirconium dioxide pearl etc. to carry out differential and loose, thereby can modulate dispersible pigment dispersion.

As jitter time, be preferably about 3～6 hours.

In addition, the differential that is undertaken by the bead processing of loosing mainly can be used the bead that is formed by glass, zirconium dioxide etc. of vertical or horizontal sand mill (sand grinder), needle mill (pin mill), slit grinding machine (slit mill), ultrasonic dispersing machine etc. and 0.01～1mm particle diameter.

In addition, about detailed content mixing, that disperse, on the books in T.C.Patton work " Paint Flow andPigment Dispersion " (John Wiley and Sons company published in 1964) etc.

In addition, (d) content of colorant is necessary for 30～60 quality % with respect to the total solid composition of cured composition for color, is preferably 35～60 quality %, more preferably 40～60 quality %.

If the concentration of colorant is when above-mentioned scope, then color depth is abundant, can effectively guarantee excellent color characteristics.

In addition, in the present invention, in using the situation of pigment derivative, as the pigment concentration of the cured composition for color among the present invention, use be the value that the gross mass with pigment and pigment derivative obtains divided by the total solid composition of cured composition for color.

((e) binder polymer)

Cured composition for color of the present invention preferably contains (e) binder polymer.

As binder polymer, it is the wire organic high molecular polymer, can from molecule (being preferably with acrylic acid series copolymer, styrene based copolymer is the molecule of main chain), have at least one alkali soluble resins that can promote alkali-soluble group (for example, carboxyl, phosphate, sulfonic group etc.) and suitably select.Wherein, more preferably solvable and alkali soluble resins that can develop by weak base aqueous solution in organic solvent.

In the preparation of alkali soluble resins, can adopt the method for for example being undertaken by known radical polymerization.Each polymerizing condition such as the kind of the temperature when preparing alkali soluble resins by radical polymerization, pressure, radical initiator and its amount, solvent types for a person skilled in the art, can easily be set, and also can be determined by experiment condition.

As above-mentioned wire organic high molecular polymer, preferably on side chain, has the polymkeric substance of carboxylic acid.For example can enumerate; open clear 59-44615 number the spy; special public clear 54-34327 number; special public clear 58-12577 number; special public clear 54-25957 number; the spy opens clear 59-53836 number; the spy opens the methacrylic acid copolymer of being put down in writing in clear 59-71048 number each communique; acrylic copolymer; itaconic acid copolymer; the crotonic acid multipolymer; maleic acid; the maleic acid of partial esterification etc.; and the acid cellulose derivant that has carboxylic acid on the side chain; have the polymkeric substance of hydroxyl and polymkeric substance that the acid anhydrides addition forms etc.; as preferred example, can also list on the side chain high molecular polymer with (methyl) acryloyl group.

Wherein, particularly preferably be (methyl) acrylic acid benzyl ester/(methyl) acrylic copolymer or by multiple copolymer that (methyl) acrylic acid benzyl ester/(methyl) acrylic acid/other monomer forms.(methyl) acrylic acid is the general name of acrylic acid and methacrylic acid, and (methyl) acryloyl group is the general name of methacryl and acryloyl group, and (methyl) acrylate is the general name of acrylate and methacrylate.

In addition, as useful polymkeric substance, can also list polymkeric substance that forms with the 2-hydroxyethyl methacrylate copolymerization etc.This polymkeric substance can use with amount mixing arbitrarily.

Except above-mentioned, can also list to open and put down in writing (methyl) acrylic acid 2-hydroxy propyl ester/polystyrene macromolecular monomer/benzyl methacrylate/methacrylic acid copolymer in the flat 7-140654 communique the spy, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester/polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromolecular monomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromolecular monomer/benzyl methacrylate/methacrylic acid copolymer etc.

For the concrete formation unit of alkali soluble resins, preferred especially (methyl) acrylic acid with can be with the multipolymer of other monomer of its copolymerization.

As above-mentioned can with other monomer of (methyl) acrylic acid copolymer, can list (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.Wherein, the hydrogen atom of alkyl and aryl also can be substituted the base replacement.

Concrete example as above-mentioned (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, benzyl acrylate, acrylic acid tolyl ester, acrylic acid naphthalene ester, cyclohexyl acrylate etc.

In addition, as above-mentioned vinyl compound, for example can list styrene, d-methyl styrene, vinyltoluene, methyl propenoic acid glycidyl base ester, vinyl cyanide, vinyl-acetic ester, N-vinyl pyrrolidone, methacrylic acid tetrahydro furfuryl ester, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer, CH ₂=CR ¹R ², CH ₂=C (R ¹) (COOR ³) [wherein, R ¹Expression hydrogen atom or carbon number are 1～5 alkyl, R ²The expression carbon number is 6～10 aromatic hydrocarbon ring, R ³The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aryl] etc.

But other monomer of these copolymerization can use a kind separately, maybe can be used in combination more than 2 kinds.But other monomer of preferred copolymerization is to be selected from CH ₂=CR ¹R ², CH ₂=C (R ¹) (COOR ³), at least a in (methyl) phenyl acrylate, (methyl) benzyl acrylate and the styrene, preferred especially CH ₂=CR ¹R ²And/or CH ₂=C (R ¹) (COOR ³).

As the content of alkali soluble resins in cured composition for color of binder polymer, with respect to the total solid composition of said composition, be preferably 1～15 quality %, more preferably 2～12 quality % are preferably 3～10 quality % especially.

((f) solvent)

Cured composition for color of the present invention, generally can be suitably by using the modulation of coming together of mentioned component and (f) solvent.

As solvent, can list, ester class, for example 3-hydracrylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, glycolic acid butyl ester, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-hydroxy methyl propionate and 3-hydracrylic acid ethyl ester; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, the ethyl carbitol acetic acid esters, acetate of butyl carbitol etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.; Ketone, for example MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.; Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.

Wherein, preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, propylene glycol methyl ether acetate etc.

Solvent can also be used in combination more than 2 kinds except can using separately.

(other composition)

In cured composition for color of the present invention, can contain sensitizing coloring matter as required, give the hydrogen compound, fluorine series organic compound, thermal polymerization, thermal polymerization prevent agent and various adjuvants such as in addition macromolecular compound of filler, above-mentioned alkali soluble resins (binder polymer), surfactant, driving fit promoter, antioxidant, ultraviolet light absorber, anti-polycoagulant.

-sensitizing coloring matter-

In cured composition for color of the present invention, can add sensitizing coloring matter as required.The exposure of the wavelength of sensitizing coloring matter through being absorbed by this sensitizing coloring matter can promote the radical initiation reaction etc. of above-mentioned Photoepolymerizationinitiater initiater and the polyreaction of the above-mentioned optical polymerism compound that causes thus.

As such sensitizing coloring matter, can list after known beam split sensitizing coloring matter or dyestuff or the absorbing light and interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

(beam split sensitizing coloring matter or dyestuff)

As the sensitizing coloring matter that uses among the present invention and preferred beam split sensitizing coloring matter or dyestuff can list, the polynuclear aromatic same clan (for example, pyrene perylene, benzophenanthrene), the xanthene class (for example, fluorescein, eosin, erythrosine, rhodamine B, rose-red), the cyanine class (for example, thia-carbonyl cyanine (thiacarbocyanine), oxa-carbocyanine (oxacarbocyanine)), the merocyanine class (for example, merocyanine, carbonyl merocyanine (carbomerocyanine)), thiazide (for example, thionine, methylenum careuleum, toluidine blue), acridine (for example, acridine orange, chloroflavin, acriflavine), phthalocyanines (for example, phthalocyanine, metal phthalocyanine), the porphyrin class (for example, tetraphenylporphyrin, the porphyrin of central metal displacement), the chlorophyll class (for example, chlorophyll, chlorophyllin, the chlorophyll of central metal displacement), metal complex (for example following compound), anthraquinone class (for example anthraquinone), squaric acid inner salt (squaryliums) class (for example, squaric acid inner salt) etc.

Following example shows the example of preferred beam split sensitizing coloring matter or dyestuff.

Can list: the styrene base system pigment of in the fair 37-13034 communique of spy, putting down in writing; Open the dye of positive ion of putting down in writing in the clear 62-143044 communique the spy; The quinoxaline salt of in the public clear 59-24147 communique of spy, putting down in writing, open the new methylene blue compound of putting down in writing in the clear 64-33104 communique the spy; Open the anthraquinone class of putting down in writing in the clear 64-56767 communique the spy; Open the benzoxanthene dye of putting down in writing in the flat 2-1714 communique the spy; Open the acridine of putting down in writing in flat 2-226148 communique and the flat 2-226149 communique of Te Kai the spy; The pyrans salt of in the public clear 40-28499 communique of spy, putting down in writing; The cyanine class of in special public clear 46-No. 42363 communiques, putting down in writing; Open the coumarone pigment of putting down in writing in flat 2-No. 63053 communiques the spy; Open the conjugation ketone pigment that flat 2-85858 communique, spy are opened flat 2-216154 communique the spy; Open the pigment of putting down in writing in the clear 57-10605 communique the spy; The azo cinnamylidene derivant of in the fair 2-30321 communique of spy, putting down in writing; Open the cyanine class pigment of putting down in writing in the flat 1-287105 communique the spy; Open the spy that clear 62-31844 communique, spy are opened clear 62-31848 communique, the spy opens the xanthene class pigment of putting down in writing in the clear 62-143043 communique; The aminobenzene vinyl ketone of in the public clear 59-28325 communique of spy, putting down in writing; Open the pigment of putting down in writing in the flat 2-179643 communique the spy; Open the merocyanine pigment of putting down in writing in the flat 2-244050 communique the spy; The merocyanine pigment of in the public clear 59-28326 communique of spy, putting down in writing; Open the merocyanine pigment of putting down in writing in the clear 59-89303 communique the spy; Open the merocyanine pigment of putting down in writing in the flat 8-129257 communique the spy; Open the benzo pyran pigment of putting down in writing in the flat 8-334897 communique the spy.

(pigment that has maximum absorption wavelength at 350～450nm)

As other preferred configuration of sensitizing coloring matter, can list the compound group and the pigment have maximum absorption wavelength at 350～450nm that belongs to following.

For example can list salt (for example squaric acid inner salt) in the polynuclear aromatic same clan (for example pyrene, perylene, benzophenanthrene), xanthene class (for example fluorescein, eosin, erythrosine, rhodamine B, rose-red), cyanine class (for example thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (for example merocyanine, carbonyl merocyanine), thiazide (for example thionine, methylenum careuleum, toluidine blue), acridine (for example acridine orange, chloroflavin (chloroflavine), acriflavine), anthraquinone class (for example anthraquinone), the squaric acid.

As the example of preferred sensitizing coloring matter, can list the compound shown in the following general formula (XIV)～(XVIII).

General formula (XIV)

In the general formula (XIV), A ¹Expression sulphur atom or NR ⁶⁰, R ⁶⁰The expression alkyl or aryl, L ⁰¹The A of expression and adjacency ¹Form the nonmetallic atom group of the alkalescence nuclear of pigment, R together with carbon atom ⁶¹, R ⁶²Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, R ⁶¹And R ⁶²Also can be bonded to each other and form the acid core of pigment.W represents oxygen atom or sulphur atom.

Below, show the preferred concrete example ((F-1)～(F-5)) of compound shown in the general formula (XIV).

General formula (XV)

In general formula (XV), Ar ¹And Ar ²Represent aryl independently of one another, be situated between by-L ⁰²-key and link.Here, L ⁰²Expression-O-or-S-.In addition, W is identical with the implication shown in the general formula (XIV).

Preference as the compound shown in the general formula (XV) can list following ((F-6)～(F-8)).

General formula (XVI)

In general formula (XVI), A ²The expression sulphur atom or-NR ⁶⁹-, L ⁰³The A of expression and adjacency ²Form the nonmetallic atom group of the alkalescence nuclear of pigment, R together with carbon atom ⁶³, R ⁶⁴, R ⁶⁵, R ⁶⁶, R ⁶⁷And R ⁶⁸The nonmetallic atom group of representing monovalence independently of one another, R ⁶⁹The expression alkyl or aryl.

Preference as the compound shown in the general formula (XVI) can list following compound ((F-9)～(F-11)).

General formula (XVII)

In general formula (XVII), A ³, A ⁴Independently of one another expression-S-or-NR ⁷³-, R ⁷³Expression replaces or the alkyl of non-replacement or the aryl of replacement or non-replacement, L ⁰⁴, L ⁰⁵Represent A independently of one another with adjacency ³, A ⁴Form the nonmetallic atom group of the alkalescence nuclear of pigment, R together with carbon atom ⁷¹, R ⁷²Represent the monovalence nonmetallic atom group independently of one another or can interosculate to form the ring of aliphatics or aromatic series.

Preference as the compound shown in the general formula (XVII) can list following compound ((F-12)～(F-15)).

In addition, in addition to these,, can also list the compound shown in the following formula (XVIII) as the preferred sensitizing coloring matter that uses among the present invention.

General formula (XVIII)

In the general formula (XVIII), A ⁵Expression can have substituent aromatic ring or heterocycle, X represent oxygen atom, sulphur atom or-N (R ⁷⁴)-, Y represent oxygen atom, sulphur atom or=N (R ⁷⁴).R ⁷⁴, R ⁷⁵, R ⁷⁶Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, A ⁵With R ⁷⁴, A ⁵With R ⁷⁵, A ⁵With R ⁷⁶Can interosculate separately and form the ring of aliphatics or aromatic series.

Here, work as R ⁷⁴, R ⁷⁵, R ⁷⁶During expression monovalence nonmetallic atom group, preferred expression replaces or does not have the alkyl or aryl of replacement.

Below, to R ⁷⁴, R ⁷⁵, R ⁷⁶Preference specifically narrate.Example as preferred alkyl, can list carbon number and be the alkyl of 1～20 straight chain shape, a chain and ring-type, as its concrete example, can list methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, icosane base, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norborny.Wherein, more preferably carbon number is that 1～12 straight chain shape, carbon number are that 3～12 chain and carbon number are the alkyl of 5～10 ring-type.

Substituting group as substituted alkyl; can use 1 valency nonmetallic atom group except hydrogen; as preference; can list; halogen atom (-F;-Br; Cl; I); hydroxyl; alkoxy; aryloxy group; sulfydryl; alkylthio group; arylthio; the alkyl disulfide group; the aryl disulfide group; amino; N-alkyl amino; N; N-dialkyl amido; N-arylamino; N; N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamoyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; N; N-dialkyl amido formyloxy; N; N-ammonia diaryl base formyloxy; N-alkyl-N-arylamino formyloxy; the alkyl sulfinyl; the aryl sulfinyl; the acyl sulfenyl; acylamino-; the N-alkyl amido; N-aryl acylamino-; the uride base; N-alkyl uride base; N; N-dialkyl group uride base; N; N-diaryl uride base; N-alkyl-N-aryl uride base; N-aryl uride base; N-alkyl-N-alkyl uride base; N; N-dialkyl group-N-alkyl uride base; N; N-dialkyl group-N-aryl uride base; N-aryl-N-alkyl uride base; N-aryl-N-aryl uride base; N; N-diaryl-N-alkyl uride base; N; N-diaryl-N-aryl uride base; N-alkyl-N-aryl-N-alkyl uride base; N-alkyl-N-aryl-N-aryl uride base; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formoxyl; acetyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formoxyl; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO ₃H) and its conjugation base (hereinafter be called " sulphonate-base), alkoxy sulfonyl, aryloxy sulfonyl, ammonia sulfinyl, N-alkyl ammonia sulfinyl, N; N-dialkyl amino sulfinyl, N-aryl ammonia sulfinyl, N; N-ammonia diaryl sulfinyl, N-alkyl-N-aryl ammonia sulfinyl, sulfamoyl, N-alkylsulfamoyl group, N; N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and its conjugation base (hereinafter be called " phosphonate (ホ ス ホ Na ト) base), dialkyl phosphine acyl group (-PO ₃(alkyl) ₂), diaryl phosphono (-PO ₃(aryl) ₂), alkylaryl phosphono (-PO ₃(alkyl) (aryl)), monoalkyl phosphono (-PO ₃H (alkyl)) and its conjugation base (hereinafter be called " alkyl phosphonic acid alkali), single aryl phosphine acyl group (-PO ₃H (aryl)) and its conjugation base (hereinafter be called " arylphosphonic acid alkali), phosphonato (-OPO ₃H ₂) and its conjugation base (hereinafter be called " phosphonate oxygen base), dialkyl phosphine acyloxy (-OPO ₃(alkyl) ₂), diaryl phosphonato (-OPO ₃(aryl) ₂), alkylaryl phosphonato (-OPO ₃(alkyl) (aryl)), monoalkyl phosphonato (-OPO ₃H (alkyl)) and its conjugation base (hereinafter be called " alkyl phosphonate oxygen base), single aryl phosphine acyloxy (-OPO ₃H (aryl)) and its conjugation base (hereinafter be called " aryl phosphine hydrochlorate oxygen base), cyano group, nitro, aryl, heteroaryl, thiazolinyl, alkynyl, silicyl.

As the concrete example of the alkyl in these substituting groups, can list abovementioned alkyl, they can also further have substituting group.

In addition; concrete example as aryl; can list phenyl; xenyl; naphthyl; tolyl; xylyl; the sym-trimethyl benzene base; isopropyl phenyl; chlorphenyl; bromophenyl; chloromethyl phenyl; hydroxy phenyl; methoxyphenyl; ethoxyl phenenyl; Phenoxyphenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; the methyl mercapto phenyl; the thiophenyl phenyl; the methylamino phenyl; dimethylamino phenyl; acetylamino phenyl; carboxyl phenyl; the methoxycarbonyl phenyl; the ethoxyl phenenyl carbonyl; the phenyloxycarbonyl phenyl; N-phenyl amino formoxyl phenyl; phenyl; cyano-phenyl; the sulfo group phenyl; the sulphonate-base phenyl; the phosphono phenyl; phosphonic acids alkali phenyl etc.

As above-mentioned heteroaryl, can use from containing nitrogen, oxygen, the monocycle of at least one in the sulphur atom, or the group that derives of Ppolynuclear aromatic ring, example as the hetero-aromatic ring in the particularly preferred heteroaryl, for example can list, thiophene, thianthrene, furans, pyrans, isobenzofuran, chromene (chromene), xanthene, phenothiazine, the pyrroles, pyrazoles, isothiazole isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, different indolizine, indoles, indazole, purine, quinolizine, isoquinoline, 2, the 3-benzodiazine, naphthyridines, quinazoline, quinoline, pteridine, carbazole, carboline, luxuriant and rich with fragrance, acridine, perimidine (Perimidine), phenanthroline, 2, the 3-benzodiazine, phenarsazine phenoxazine, furazan phenoxazine etc., they also can be fused benzo rings, and also can have substituting group.

In addition,, can list vinyl, 1-propenyl, 1-butenyl group, cinnamyl, 2-chloro-1-vinyl etc. as the example of thiazolinyl.In addition, as the example of alkynyl, can list ethinyl, 1-propinyl, 1-butynyl, trimethyl silyl ethinyl etc.As acyl group (G ¹CO-) in G ¹, can list hydrogen and above-mentioned alkyl, aryl.In these substituting groups; as preferred; can list halogen atom (-F;-Br;-Cl;-I); alkoxy; aryloxy group; alkylthio group; arylthio; N-alkyl amino; N; N-dialkyl amido; acyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; acylamino-; formoxyl; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; sulfo group; sulphonate-base; sulfamoyl; the N-alkylsulfamoyl group; N, the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; phosphono; the phosphonic acids alkali; the dialkyl phosphine acyl group; the diaryl phosphono; the monoalkyl phosphono; the alkyl phosphonic acid alkali; single aryl phosphine acyl group; the arylphosphonic acid alkali; phosphonato; phosphonate oxygen base; aryl; thiazolinyl; alkylidene radical (methylene etc.).

On the other hand, as the alkylidene in the substituted alkyl, can enumerate and slough above-mentioned carbon number is the organic residue of divalent that obtains behind arbitrary hydrogen atom on 1 to 20 the alkyl, can preferably enumerate carbon number and be 1 to 12 straight chain shape, carbon number and be 3 to 12 chain and carbon number and be the alkylidene of 5 to 10 ring-type.

As R by the combination of above-mentioned substituting group and alkylidene is obtained ⁷⁴, R ⁷⁵, or R ⁷⁶The concrete example of preferred substituted alkyl; can list chloromethyl; bromomethyl; the 2-chloroethyl; trifluoromethyl; methoxy; methoxyethoxyethyl; allyl oxygen ylmethyl; phenoxymethyl; methylthiomethyl; toluene sulfenyl methyl; the ethylamino ethyl; the lignocaine propyl group; morpholinyl propyl; acetoxy-methyl; benzoyl oxygen ylmethyl; N-cyclohexyl carboxyamide base oxygen base ethyl; N-phenyl amino formoxyl oxygen base ethyl; the acetylamino ethyl; N-methyl benzoyl aminopropyl; the 2-oxoethyl; the 2-oxopropyl; the carboxyl propyl group; the methoxycarbonyl ethyl; allyl oxygen base carbonyl butyl; chlorophenoxy carbonyl methyl; the carbamyl ylmethyl; N-methylamino formoxyl ethyl; N; N-dipropyl carbamyl ylmethyl; N-(methoxyphenyl) carbamyl ethyl; N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl; the sulfo group butyl; the sulphonate-base propyl group; the sulphonate-base butyl; the amino-sulfonyl butyl; N-ethylamino sulfonyl methyl; N, N-dipropyl amino-sulfonyl propyl group; N-tolyl amino-sulfonyl propyl group; N-methyl-N-(phosphono phenyl) amino-sulfonyl octyl group; the phosphono butyl; phosphonic acids alkali hexyl; the diethyl phosphonyl butyl; diphenylphosphine acyl group propyl group; methylphosphine acyl group butyl; methylphosphonic acid alkali butyl; tolylphosphine acyl group hexyl; tolylphosphine hydrochlorate base hexyl; the phosphonato propyl group; phosphonic acids alkali oxygen Ji Dingji; benzyl; phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenylethyl; to methyl-benzyl; cinnamyl; allyl; 1-propenyl methyl; the 2-butenyl group; the 2-methacrylic; 2-metering system ylmethyl; 2-propynyl; the 2-butynyl; 3-butynyl etc.

As R ⁷⁴, R ⁷⁵, or R ⁷⁶And the concrete example of preferred aryl groups can list, can enumerate and form condensed ring by 1 to 3 phenyl ring and the group that obtains, form condensed ring and the group that obtains by phenyl ring and five yuan of unsaturated rings, as concrete example, can enumerate phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl, wherein more preferably phenyl, naphthyl.

As R ⁷⁴, R ⁷⁵, or R ⁷⁶And the concrete example of preferred substituted aryl, the group that can use on the one-tenth ring carbon atom of above-mentioned aryl and have (except that hydrogen atom) 1 valency nonmetallic atom group is as substituent substituted aryl.As the example of preferred substituted, can list above-mentioned alkyl, substituted alkyl and front as the group shown in the substituting group on the substituted alkyl.Preferred concrete example as this type of substituted aryl; can list; xenyl; tolyl; xylyl; the sym-trimethyl benzene base; isopropyl phenyl; chlorphenyl; bromophenyl; fluorophenyl; chloromethyl phenyl; trifluoromethyl; hydroxy phenyl; methoxyphenyl; the methoxy ethoxy phenyl; allyl oxygen base phenyl; Phenoxyphenyl; the methyl mercapto phenyl; tolyl sulfenyl phenyl; the ethylamino phenyl; the lignocaine phenyl; the morpholinyl phenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; N-cyclohexyl carboxyamide base oxygen base phenyl; N-phenyl amino formoxyl oxygen base phenyl; the acetyl-amino phenyl; N-methyl benzoyl aminophenyl; carboxyl phenyl; the methoxycarbonyl phenyl; allyl oxygen base carbonyl phenyl; the chlorophenoxy carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl; N; N-dipropyl carbamyl phenyl; N-(methoxyphenyl) carbamyl phenyl; N-methyl-N-(sulfo group phenyl) carbamyl phenyl; the sulfo group phenyl; the sulphonate-base phenyl; the amino-sulfonyl phenyl; N-ethylamino sulfonyl phenyl; N, N-dipropyl amino-sulfonyl phenyl; N-tolyl amino-sulfonyl phenyl; N-methyl-N-(phosphono phenyl) amino-sulfonyl phenyl; the phosphono phenyl; phosphonic acids alkali phenyl; the diethyl phosphonyl phenyl; diphenylphosphine acyl group phenyl; methylphosphine acyl group phenyl; methylphosphonic acid alkali phenyl; tolylphosphine acyl group phenyl; tolylphosphine hydrochlorate base phenyl; allyl phenyl; 1-propenyl aminomethyl phenyl; 2-butenyl group phenyl; 2-methacrylic phenyl; 2-methylpropenyl phenyl; the 2-propynyl phenyl; 2-butynyl phenyl; 3-butynyl phenyl etc.

In addition, as R ⁷⁵And R ⁷⁶More preferably example, can list the alkyl that replaces or do not have replacement.In addition, as R ⁷⁴More preferably example, can list the aryl that replaces or do not have replacement.Its reason is not determined as yet, but infer be because, by having such substituting group, because of electron excitation state that light absorption produced and the interaction of initiator compounds become big especially, thereby improved the cause that initiator compounds produces the efficient of free radical, acid or alkali.

Below, the A in the mutual-through type (XVIII) ⁵Describe.A ⁵Expression can have substituent aromatic rings or heterocycle, as the concrete example that can have substituent aromatic rings or heterocycle, can list the R at mutual-through type (XVIII) ⁷⁴, R ⁷⁵Or R ⁷⁶Above-mentioned explanation in the listed same example of enumerating.

Wherein, as preferred A ⁵, can list have alkoxy, sulfane base, amino aryl, as particularly preferred A ⁵, can list aryl with amino.

Below, the Y in the mutual-through type (XVIII) describes.Y be situated between by two keys with general formula (XVIII) in direct-connected non-metallic atom of nitrogen heterocyclic ring or nonmetallic atom group, expression oxygen atom, sulphur atom or=N (R ⁷⁴).

In addition, the X in the general formula (XVIII) represent oxygen atom, sulphur atom or-N (R ⁷⁴)-.

Below, be that the compound shown in the general formula (XVIII-1) describes to the preferred configuration of compound shown in the general formula (XVIII) that uses among the present invention.

General formula (XVIII-1)

In above-mentioned general formula (XVIII-1), A ⁵Expression can have substituent aromatic rings or heterocycle, X represent oxygen atom or sulphur atom or-N (R ⁷⁴)-.R ⁷⁴, R ⁷⁷, R ⁷⁸Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, A ⁵With R ⁷⁴, A ⁵With R ⁷⁷, A ⁵With R ⁷⁸Can interosculate respectively to form the ring of aliphatics or aromatic series.Ar represents to have substituent aromatic rings or heterocycle.But the substituting group on the Ar skeleton, the summation of its Hammett value (Hammett ' substituent Constant) needs bigger than 0.Here, " summation of Hammett value is bigger than 0 " is meant to have a substituting group, and this substituent Hammett value is bigger than 0, also can have a plurality of substituting groups, and the summation of these substituent Hammett values is bigger than 0.

In general formula (XVIII-1), A ⁵And R ⁷⁴Identical with the implication in the general formula (XVIII), R ⁷⁷With the R in the general formula (XVIII) ⁷⁵Implication is identical, R ⁷⁸With the R in the general formula (XVIII) ⁷⁶Implication is identical.In addition, Ar represents to have substituent aromatic rings or heterocycle, with the A in the general formula (XVIII) ⁵Implication is identical.

But, as the substituting group on the Ar that can import to general formula (XVIII-1), the summation of Hammett value is required to be more than 0, as this type of substituent example, can list trifluoromethyl, carbonyl, ester group, halogen atom, nitro, cyano group, sulfoxide group, amide group, carboxyl etc.Show these substituent Hammett values below.Can list: trifluoromethyl (-CF ₃, m:0.43, p:0.54), carboxyl (for example-COH, m:0.36, p:0.43), ester group (-COOCH ₃, m:0.37, p:0.45), halogen atom (for example Cl, m:0.37, p:0.23), cyano group (-CN, m:0.56, p:0.66), sulfoxide group (for example-SOCH ₃, m:0.52, p:0.45), amide group (for example-NHCOCH ₃, m:0.21, p:0.00), carboxyl (-COOH, m:0.37, p:0.45) etc.Expression is that this substituting group imports to position and its Hammett value on the aryl skeleton in the bracket, (m:0.50) represent this substituting group import between Hammett value during the position be 0.50.Wherein,, can list and have substituent phenyl,, can list ester group, cyano group as the preferred substituents on the Ar skeleton as the preference of Ar.Position as replacing is preferably placed at the ortho position on the Ar skeleton especially.

Show the preferred concrete example (exemplary compounds (F1)～exemplary compounds (F56), but the present invention is not as limit of the sensitizing coloring matter shown in the general formula involved in the present invention (XVIII) below.

In the present invention's above-mentioned sensitizing coloring matter applicatory,, be preferably the compound shown in the above-mentioned general formula (XVIII) from the viewpoint of deep curable.

About above-mentioned sensitizing coloring matter,, can carry out following such various chemical modifications in order to improve the characteristic of cured composition for color of the present invention.For example; (for example make sensitizing coloring matter and addition polymerization compound structure by methods such as covalent bond, ionic link, hydrogen bonds; acryloyl group or methacryl) combination, can obtain the crosslinking curing film high strength, improve the unnecessary inhibition effect separated out of pigment from the crosslinking curing film.

The content of sensitizing coloring matter is preferably 0.01～20 quality % with respect to the total solid composition of cured composition for color, more preferably 0.01～10 quality %, more preferably 0.1～5 quality %.

Content by making sensitizing coloring matter is in this scope, and then sensitivity height under the exposure wavelength of ultrahigh pressure mercury lamp can obtain film deep curable, and forms the aspect of property from Development margin (margin), pattern, is preferred.

-give the hydrogen compound-

Cured composition for color of the present invention preferably contains to the hydrogen compound.The hydrogen compound of giving among the present invention has following effects, promptly further improves sensitizing coloring matter or the Photoepolymerizationinitiater initiater sensitivity to active radioactive ray, or suppresses oxygen to the polymerization obstruction of polymerizable compound etc.

As such example of giving the hydrogen compound; can list amine; for example " the Journal of Polymer Society " the 10th that delivers people such as M.R.Sander rolls up 3173 pages (1972); special public clear 44-20189 communique; the spy opens clear 51-82102 communique; the spy opens clear 52-134692 communique; the spy opens clear 59-138205 communique; the spy opens clear 60-84305 communique; the spy opens clear 62-18537 communique; the spy opens clear 64-33104 communique; the compound of record etc. among No. 33825, the Research Disclosure can list triethanolamine particularly; (dimethylamino)-ethyl benzoate; to the formoxyl xylidin; to methyl mercapto xylidin etc.

As other the example of giving the hydrogen compound, mercaptan and thioether class are arranged, for example can list and to open clear 53-702 communique, special public clear 55-500806 communique, spy the spy and open the mercaptan compound of putting down in writing in the flat 5-142772 communique, open disulfide compound in the clear 56-75643 communique etc. the spy, can list 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc. particularly.

In addition, as other example of giving the hydrogen compound, the organometallics of can list amino-acid compound (for example N-phenylglycine etc.), in the public clear 48-42965 communique of spy, putting down in writing (for example tributyl tin acetic acid esters etc.), the hydrogen donor of in the public clear 55-34414 communique of spy, putting down in writing, open the sulphur compound put down in writing in the flat 6-308727 communique (for example trithiane etc.) etc. the spy.

These give the content of hydrogen compound, from improve the viewpoint of curing rate by the balance between aggregation growth speed and the chain transfer, quality optimization with respect to the total solid composition of cured composition for color is the scope of 0.1～30 quality %, the more preferably scope of 0.5～25 quality %, the more preferably scope of 1～20 quality %.

-fluorine series organic compound-

Cured composition for color of the present invention can also contain the fluorine series organic compound.

By containing this fluorine series organic compound, can improve the characteristics of liquids (particularly mobile) when cured composition for color of the present invention made coating fluid, and can improve coating thickness homogeneity, economize fluidity.That is to say, by reducing applied the surface tension with coating fluid, thereby improve wetting state to applied, raising is to applied coating, therefore, even in the situation of the film that forms several μ m degree with a spot of liquid measure, also can effectively form the film of less uniform thickness in uneven thickness.

The fluorine containing ratio of fluorine series organic compound is preferably 3～40 quality %, more preferably 5～30 quality %, preferred especially 7～25 quality %.The fluorine containing ratio is in above-mentioned scope the time, the coating thickness homogeneity and economize fluidity aspect be that effectively the dissolubility in composition is also good.

As the fluorine series organic compound, can list for example MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACEF141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437 (above is Dainippon Ink. ﹠ Chemicals Inc's system), FLUORADFC430, FLUORADFC431, FLUORADFC171 (above is Sumitomo ス リ-エ system Co., Ltd. system), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, SurflonSC-383, Surflon S393, Surflon KH-40 (above is Asahi Glass Co., Ltd's system) etc.

As mentioned above, the fluorine series organic compound is effective when preventing crawling when coated film is thin and uneven thickness especially.When using in the slot coated that easily causes the liquid cutout in addition, also is effective.

The addition of fluorine series organic compound is preferably 0.001～2.0 quality % with respect to the all-mass of cured composition for color, more preferably 0.005～1.0 quality %.

-thermal polymerization-

Make that to contain thermal polymerization in the cured composition for color of the present invention also be effective.As thermal polymerization; can list for example various azo based compounds, superoxide based compound; as above-mentioned azo based compound; can list the bisdiazo based compound; as above-mentioned superoxide based compound, can list ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate etc.

-surfactant-

From the viewpoint of improvement coating, cured composition for color of the present invention preferably uses various surfactants to constitute, and can use the various surfactants of nonionic system, kation system, negative ion system.Wherein, preferred nonionic is that the fluorine that has perfluoroalkyl in the surfactant is a surfactant.

As fluorine is the concrete example of surfactant, can list MEGAFACE (registered trademark) series of Dainippon Ink. ﹠ Chemicals Inc's system, FLUORAD (registered trademark) series of 3M corporate system etc.

In addition, can also use phthalocyanine derivates (commercially available product EFKA-745 (gloomy industry corporate system down)); Organic siloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic acid series (being total to) polymkeric substance Port リ Off ロ-No.75, No.90, No.95 (oil chemistry industrial group of common prosperity society system), W001 cationic surfactants such as (abundant merchant's corporate systems); Polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty ester nonionics such as (BASF AG's system, Pluronic L10, L31, L61, L62,10R5,17R2,25R2, テ ト ロ ニ Star Network (TETRONIC) 304,701,704,901,904,150R1) are surfactant; W004, W005, W017 negative ion such as (abundant merchant's corporate systems) are surfactant etc.

-other additive-

Except above-mentioned substance,, can list filling agents such as glass, aluminium oxide as the concrete example of additive; The soluble resin of alkali such as phenoxy resin that the polymkeric substance of the maleic acid of itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification, acid cellulose derivant, the polymkeric substance with hydroxyl and acid anhydrides addition, alcohol soluble nylon, bisphenol-A and chloropropylene oxide form; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (above is gloomy industry corporate system down), デ イ ス パ-ス エ イ De 6, デ イ ス パ-ス エ イ De 8, デ イ ス パ-ス エ イ De 15, デ イ ス パ-ス エ イ De 9100 macromolecule dispersing agents such as (being San nopco corporate system); Various SOLSPERSE spreading agents (above is Lubrizol Co., Ltd. system) such as SOLSPERSE 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; ADEKAPluronicL31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above be rising sun electrification corporate system) and Isonet S-20 (above change into corporate system for Sanyo); Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; And anti-polycoagulant such as sodium polyacrylate.

In addition, promote the alkali solubility of uncured portion, further improve in the situation of development of cured composition for color in desire, can add organic carboxyl acid in cured composition for color, preferably add molecular weight is low-molecular-weight organic carboxyl acid below 1000.

As organic carboxyl acid, specifically for example can list formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid; Benzoic acid, methyl benzoic acid, isopropyl acid, 2,3-mesitylenic acid, 3, aromatic monocarboxylates such as 5-mesitylenic acid; Aromatic series polybasic carboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, phenylpropionic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, phenylacrylic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, Chinese cassia tree fork guanidine-acetic acid, coumaric acid, umbellic acid.

-thermal polymerization prevent agent-

In cured composition for color of the present invention, except above-mentioned substance, can also add thermal polymerization and prevent agent.

Prevent agent as thermal polymerization, p-dihydroxy-benzene, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, the tert-butyl group connect benzenediol, benzoquinones, 4,4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc. are useful.

(modulation of cured composition for color)

Cured composition for color of the present invention can be by containing above-mentioned (a)～(d), and then adjuvant such as mixed solvent, surfactant as required, thereby modulate.

In addition, be in the situation of pigment at (d) colorant, the conditioned pigment dispersion liquid uses this dispersible pigment dispersion to obtain cured composition for color of the present invention then at first as described above.

When using in the modulation at cured composition for color of the present invention in the situation of dispersible pigment dispersion, its content is with respect to the total solid composition (quality) of cured composition for color, preferred pigments content is more than the 30 quality % and the amount of the scope below the 60 quality %, more preferably pigment content is more than the 35 quality % and the amount of the scope below the 60 quality %, and further preferred pigments content is more than the 40 quality % and the amount of the scope below the 60 quality %.

When the content of dispersible pigment dispersion was in this scope, color depth was abundant, can effectively guarantee excellent color characteristics.

＜color filter and manufacture method thereof 〉

Color filter of the present invention is characterised in that, has the colored pattern that the cured composition for color by the invention described above forms on substrate.

In addition, manufacturing method of color filter of the present invention is characterised in that, uses the cured composition for color of the invention described above, through be coated with repeatedly, prebake conditions, exposure and development form colored pattern arbitrarily.

Below, to color filter of the present invention, specifically narrate by its manufacture method (manufacturing method of color filter of the present invention).

Manufacturing method of color filter of the present invention as mentioned above, has each operation of coating, prebake conditions, exposure and development.By via these operations, can form colored pattern by the pixel formation of shades of colour (3 looks or 4 looks), obtain color filter.

By using such method, the color filter that can under the little situation of technologic difficulty, in liquid crystal display cells and solid-state imager, use with high-quality and low-cost production.

Below, each operation is elaborated.

(painting process)

At first, the substrate that uses in the painting process is described.

As the substrate that uses in the color filter of the present invention, for example can list: be used for alkali-free glass, the soda-lime glass of liquid crystal display cells etc., the glass of sending lachs (PYREX) (registered trademark) glass, quartz glass and on them, having attached nesa coating, the perhaps photo-electric conversion element substrate that in solid-state imager etc., uses, for example silicon substrate etc., and plastic base.

On these substrates, can be formed with the black matrix" of isolating each pixel or be provided for promoting the transparent resin layer of driving fit etc.

In addition, on plastic base, preferably have gas-barrier layer and/or solvent resistance layer in its surface.

In addition, the driving of disposing thin film transistor (TFT) (TFT) that also can use thin film transistor (TFT) (TFT) formula color liquid crystal display arrangement is with substrate (hereinafter being called " TFT formula liquid crystal drive substrate "), on this drives with substrate, use cured composition for color of the present invention to form colored pattern, make color filter.

With the substrate in the substrate, can list for example glass, polysiloxane, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc. as TFT formula liquid crystal drive.Suitable pre-treatments such as the chemical reagent processing of as required, can be in advance these substrates being implemented to be undertaken by silane coupling agent etc., Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation.For example, also can use the substrate that on the surface of TFT formula liquid crystal drive, has formed passivation such as silicon nitride film (passivation) film with substrate.

In painting process, method as coating cured composition for color of the present invention on substrate, there is not particular determination, preferred slit-rotary process, the method for use gap nozzle such as (non-spin) rubbing method (hereinafter be called " gap nozzle rubbing method) without spin.

In the gap nozzle rubbing method, slit-rotary process, rubbing method without spin, size condition difference because of coated substrates, for example, (in the situation of 1100mm * 1250mm), be generally for 500～2000 microlitre/seconds at the glass substrate that uses rubbing method without spin to be coated on for the 5th generation from the spray volume of the cured composition for color of gap nozzle, 800～1500 microlitre/seconds more preferably, in addition, coating speed is generally 50～300mm/ second, is preferably 100～200mm/ second.

In addition,, be generally 10%～20%, be preferably 13%～18% as the solid constituent of the cured composition for color that uses in the painting process.

On substrate, form by cured composition for color of the present invention obtain film the time, as this thickness of filming (prebake conditions is handled the back), be generally 0.3 μ m～5.0 μ m, be preferably 0.5 μ m～4.0 μ m, most preferably be 0.5 μ m～3.0 μ m.

In addition, when using under the situation of color filter for solid-state imager, the thickness of filming (prebake conditions is handled the back) is preferably the scope of 0.5 μ m～5.0 μ m.

In painting process, after coating, implement prebake conditions usually and handle.As required, can also before prebake conditions, implement application of vacuum.

Vacuum drying condition is that vacuum tightness is generally 0.1torr～1.0torr, is preferably about 0.2torr～0.5torr.

In addition, prebake conditions is handled and can be used heating plate, baking oven etc. to carry out in 50 ℃～140 ℃ temperature range, under preferred about 70 ℃～110 ℃, 10 seconds～300 seconds condition.In addition, this prebake conditions handle can and with the high frequency processing etc.High frequency is handled and also can be used separately.

(exposure process)

In the exposure process, to form as mentioned above by filming that cured composition for color forms, expose by the mask pattern of stipulating.

The radioactive ray that use during as exposure, ultraviolet rays such as preferred especially g line, h line, i line, j line.

In addition, when making liquid crystal indicator and use color filter, preferably utilize proximity (proximity) exposure machine, mirror image projection exposure machine mainly to use the exposure of h line, i line.

In addition, when the manufacturing solid-state imager is used color filter, preferably utilize step-by-step exposure machine, mainly use the i line.

In addition, when using TFT mode liquid crystal drive to make color filter with substrate, the photomask of use also is provided for forming through hole or コ font depressed patterns except being provided for forming the pattern of pixel (colored pattern).

(developing procedure)

In the developing procedure, make uncured the stripping of filming after the exposure in developer solution, only residual cured portion on substrate.

As development temperature, be generally 20～30 ℃, as development time, be 20～90 seconds.

As developer solution, do not dissolve the developer solution of solidified portion so long as dissolve the filming of cured composition for color of uncured portion, just can use any developer solution.

Particularly, can use the combination or the alkaline aqueous solution of various organic solvents.

As the organic solvent that uses in developing, can enumerate the above-mentioned solvent that when modulation cured composition for color of the present invention, can use.

In addition, as alkaline aqueous solution, for example can enumerate NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-alkali compounds such as 7-hendecene with concentration reach 0.001 quality %～10 quality %, the mode that is preferably 0.01 quality %～1 quality % is dissolved and the alkaline aqueous solution that obtains.

In alkaline aqueous solution, also can add an amount of water-miscible organic solvent such as for example methyl alcohol, ethanol etc. or surfactant etc.

Visualization way can be in impregnation method, spray mode, the spray pattern etc. any, also can make up swing mode, rotation mode, ultrasound wave mode etc. in these modes.Before the contact developer solution, also can water in advance etc. the wetting face that is developed, it is uneven to prevent to develop.In addition, also can make substrate tilt to develop.

When the color filter that the manufacturing solid-state imager is used, also can adopt oar formula (paddle) to develop.

After the development treatment, remove the flushing of remaining developer solution through washing and handle, implement dry.

Flushing is handled and is carried out with pure water usually, but in order to save liquid, can use pure water when final washing, then uses the pure water of using at the washing initial stage, perhaps makes substrate tilt to wash, and perhaps also can and use ultrasonic irradiation.

(heat treated)

After aforesaid drying, carry out 100 ℃～250 ℃ heat treated usually.

Can use heating plate or heater meanses such as convection oven (the circulating dryer of warm braw), high frequency heating machine according to above-mentioned condition, filming after developing be carried out this heat treated (back baking) with continous way or batch (-type).

Back baking like this be for reach make completion of cure purpose and make to develop after the operation of pattern form purpose of positive taperization by thermal deformation, carry out 200 ℃～250 ℃ heating (toasting firmly) usually.

Cured composition for color of the present invention is by containing (a)～(d) composition, in heating process, can make pattern form after the development by thermal deformation positive taperization, make its heat curing then, consequently, can form fine and have good cross sectional shape and colored pattern that hardness is high.

According to desirable form and aspect number, successively each color is carried out above each operation repeatedly, can make the color filter of the cured film (colored pattern) that is formed with multiple color dyes.

As the purposes of cured composition for color of the present invention, main is that the center is illustrated with the purposes in the colored pattern of color filter, also goes for the formation of black matrix" that the colored pattern (pixel) that constitutes color filter is isolated.

Use contains the cured composition for color of the processed pigment of black pigments such as carbon black, titanium be black, through coating, exposure and each operation of developing, carries out back then as required to toast, and just can form the black matrix" on the substrate.

＜liquid crystal indicator 〉

Liquid crystal indicator of the present invention has color filter of the present invention.

More particularly, being by forming alignment films in the inner face side of color filter of the present invention, and making alignment films and electrode base board opposed, fill liquid crystal and seal at gap portion, is panel thereby obtain liquid crystal indicator of the present invention.

[embodiment]

Below, be described more specifically the present invention by embodiment, still, only otherwise break away from purport of the present invention, be not limited to following embodiment.In addition, do not having under the situation about specifying, " part " is benchmark with the quality.

(embodiment 1)

The preparation of＜cured composition for color 1 〉

The composition of following composition is mixed, stir with rotating speed 3000r.p.m. with homogenizer and mixed in 3 hours, preparation contains the mixed solution of pigment.

(composition)

70 parts of pigment green 36s (average primary particle diameter is 25nm)

30 parts of pigment yellows 150 (average primary particle diameter is 25nm)

10 parts of phthalocyanine derivates

(SOLSPERSE 3000, Avecia Co., Ltd. system)

75 parts of the propylene glycol methyl ether acetate solution (solid constituent 40%) of benzyl methacrylate/methacrylic acid (=70/30[mol ratio]) multipolymer (Mw is 5,000)

35 parts of spreading agents (BYK-161, BYK corporate system)

495 parts of propylene glycol methyl ether acetates

Then, further the bead dispersion machine (dispermat) (GETZMANN corporate system) of the zirconium dioxide pearl by having used 0.3mm φ carries out 6 hours dispersion treatment to the above-mentioned mixed solution that obtains.Further use the high pressure dispersion machine NANO-3000-10 that has the mechanism of decompressor (Japanese BEE Co., Ltd. system) then, at 2000kg/cm ³Pressure under, carry out dispersion treatment with 500g/ minute flow.Repeat this dispersion treatment 10 times, obtain the viridine green dispersive composition.

In the viridine green dispersive composition that obtains, further add the composition of following composition, mix, thereby modulate cured composition for color 1 of the present invention (colored resist liquid).In addition, the pigment concentration in the total solid composition of the cured composition for color 1 of gained is 48%.

(composition)

30 parts of the exemplary compounds A-1 of record in the above-mentioned table 1

(the system A-BPE-4 of Xin Zhong village chemical industrial company, specific 2 functional monomers)

2-(Chloro-O-Phenyl)-4,10 parts of 5-diphenyl-imidazole dipolymers

(Photoepolymerizationinitiater initiater)

5 parts of 4,4 '-two (lignocaine) benzophenone (sensitizing coloring matter)

5 parts of 2-mercaptobenzothiazoles (giving the hydrogen compound)

5 parts of EHPE3150

(Daicel chemical company system, thermal cross-linking agent, softening point: 60～90 ℃, epoxide equivalent: 180, molecular weight: 2234)

230 parts of propylene glycol methyl ether acetates

In addition, the pigment concentration in the cured composition for color 1 calculates according to as described below.

Pigment (PG36+PY150+ phthalocyanine derivates)=110 parts

Solid constituent=pigment (110 parts)+benzyl methacrylate/methacrylic acid copolymer (75 * 0.4=30 part)+spreading agent (35 parts)+55 parts (specific 2 functional monomers+Photoepolymerizationinitiater initiater+sensitizing coloring matter+to hydrogen compound+thermal cross-linking agent)=230 parts

Pigment concentration=110/230 * 100=48%

(embodiment 2)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to the exemplary compounds A-2 of record in the above-mentioned table 1, carry out similarly to Example 1, make obtaining cured composition for color 2.

(embodiment 3)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to the exemplary compounds A-3 of record in the above-mentioned table 1, carry out similarly to Example 1, make obtaining cured composition for color 3.

(embodiment 4)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to the exemplary compounds A-4 of record in the above-mentioned table 1, carry out similarly to Example 1, make obtaining cured composition for color 4.

(embodiment 5)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to the exemplary compounds A-5 of record in the above-mentioned table 1, carry out similarly to Example 1, make obtaining cured composition for color 5.

(embodiment 6)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to the exemplary compounds A-6 of record in the above-mentioned table 1, carry out similarly to Example 1, make obtaining cured composition for color 6.

(embodiment 7)

Except the thermal cross-linking agent that will be among the embodiment 1 uses is the EPICLON N-660 (softening point: 60～90 ℃ that EHPE3150 replaces to the big Japanese ink chemical industry system of following structure, epoxide equivalent: 190～250, molecular weight: 3400), carry out fully similarly to Example 1, make obtaining cured composition for color 7.

(embodiment 8)

Except the thermal cross-linking agent that will be among the embodiment 1 uses is the HXA-4700 (softening point: 85～98 ℃ that EHPE3150 replaces to the big Japanese ink chemical industry system of following structure, epoxide equivalent: 155～170), carry out fully similarly to Example 1, make obtaining cured composition for color 8.

(comparative example 1)

The preparation of＜cured composition for color R1 〉

Prepare cured composition for color R1 based on following composition.

The composition of＜cured composition for color R1 〉

The barium sulphate dispersion liquid ⁽¹⁾66.7 part

36.38 parts of PR300

(the clear and epoxy acrylate solid constituent macromolecule corporate system is a propylene glycol methyl ether acetate solution 68%, that contain 3% ソ Le ベ Star ソ 150)

76% propylene glycol methyl ether acetate solution of dipentaerythritol acrylate

20.96 part

5.07 parts of IRGACURE819 (Ciba Specialty Chemicals corporate system)

7.36 parts of エ ピ Network ロ Application EXA850S (big Japanese ink corporate system)

1.45 parts of DICY7 (four countries change into corporate system)

0.41 part of 2MAOK (four countries change into corporate system)

0.17 part of 30% methyl ethyl ketone solution of F780F (big Japanese ink corporate system)

The blue pigment dispersion liquid ⁽²⁾1.0 part

40 parts of MEKs

(1) in advance with barium sulphate (Sakai chemical company system, B30) 30 parts, above-mentioned phenylethylene/maleic anhydride/butyl acrylate copolymer (mol ratio: 40/32/28) with after 35.71 parts of 34.29 parts of 35% methyl ethyl ketone solutions of the addition reaction of benzylamine (anhydride group with respect to this multipolymer is 1.0 equivalents), acetate 1-methoxyl-2-propyl diester mix, with electronic grinding machine M-200 (ア イ ガ-corporate system), use the zirconium dioxide pearl of diameter, disperse to be prepared in 3.5 hours with the peripheral speed of 9m/s as 1.0mm.

(2) in advance with blue pigment (HELIOGEN BLUE L6700F; C.I. pigment blue 15: after 6) 14 parts, 13.79 parts of above-mentioned PR300 (solid constituent 68% solution), 112.21 parts of mixing of propylene glycol methyl ether acetate, with electronic grinding machine M-200 (ア イ ガ-corporate system), use the zirconium dioxide pearl of diameter, disperse to be prepared in 180 minutes with the peripheral speed of 9m/s as 0.3mm.

In addition, the as described below calculating of pigment concentration among the cured composition for color R1.

Pigment (PB15:1)=0.1 part

Solid constituent=pigment (0.1 part)+barium sulphate (20 parts)+bonding agent (8 parts)+thermal cross-linking agent (24.8 parts)+other (30.3 parts)=83.2 parts

Pigment concentration=0.1/83.2 * 100=0.12%

(comparative example 2)

The preparation of＜cured composition for color R2 〉

The cured composition for color R2 for preparing as described below.

(Resin A synthetic that comprises structure) with free-radical polymerised group

20 parts of cresols linear phenol-aldehyde resins " EP4050G " (the organic material corporate system of the rising sun)

100 parts of cyclohexanone

Above-mentioned material is mixed, and then to add with respect to the hydroxyl of cresols linear phenol-aldehyde resin be (methyl) acryloxyalkyl isocyanates (clear and electrician's corporate system of 20 moles of %, trade name: " カ レ Application ズ MOI "), 0.1 part (catalyzer (triethylamine)), 60 ℃ of reactions 6 hours down.

The compound that obtains is precipitated with chloroform solvent again, thereby make with extra care, obtain comprising the Resin A of structure with free-radical polymerised group.Decision with importing rate of free-radical polymerised compound is by carrying out the mensuration of 1H-NMR, is 20% by area than definite hydroxyl with respect to the cresols linear phenol-aldehyde resin then.Then, use this Resin A that comprises structure, each material is mixed, carry out fully mixingly with three-roll mill, make cured composition for color R2 according to following ratio of components with free-radical polymerised group.

(composition of cured composition for color R2)

20 parts of Resin A that comprise structure with free-radical polymerised group

400 parts of cyclohexanone (with the pure medicine corporate system of light)

20 parts of photo polymerization monomers

(pentaerythritol triacrylate (Osaka organic chemistry corporate system, trade name " V#300 "))

0.6 part of Photoepolymerizationinitiater initiater

(Ciba Specialty Chemicals corporate system, ProductName " IRGACURE369 ")

90 parts of carbon pigment " MA-8 " (the マ テ リ ア of Mitsubishi Le corporate system)

0.9 part of spreading agent " SOLSPERSE#5000 " (Zeneca corporate system)

0.5 part of fluorochemicals (big Japanese ink chemical company system, ProductName " F179 ")

In addition, the pigment concentration among the cured composition for color R2 calculates according to following.

Carbon pigment=90 part

Solid constituent=carbon pigment (90 parts)+comprise Resin A (20 parts)+spreading agent (0.9 part)+monomer, initiating agent, the surfactant (21.1 parts)=132 parts of structure with free-radical polymerised group

Pigment concentration=90/132 * 100=68%

(comparative example 3)

The preparation of＜cured composition for color R3 〉

The composition of following composition is mixed, stir with rotating speed 3000r.p.m. with homogenizer and mixed in 3 hours, preparation contains the mixed solution of pigment.

(composition)

70 parts of pigment green 36s (average primary particle diameter is 25nm)

30 parts of pigment yellows 150 (average primary particle diameter is 25nm)

10 parts of phthalocyanine derivates

(SOLSPERSE 3000, Avecia Co., Ltd. system)

75 parts of the propylene glycol methyl ether acetate solution (solid constituent 40%) of benzyl methacrylate/methacrylic acid (=70/30[mol ratio]) multipolymer (Mw is 5,000)

35 parts of spreading agents (BYK-161, BYK corporate system)

495 parts of propylene glycol methyl ether acetates

Then, further the bead dispersion machine (GETZMANN corporate system) of the zirconium dioxide pearl by having used 0.3mm φ carries out 6 hours dispersion treatment to the above-mentioned mixed solution that obtains.Further use the high pressure dispersion machine NANO-3000-10 that has the mechanism of decompressor (Japanese BEE Co., Ltd. system) then, at 2000kg/cm ³Pressure under, carry out dispersion treatment with 500g/ minute flow.Repeat this dispersion treatment 10 times, obtain the viridine green dispersive composition.

In the viridine green dispersive composition that obtains, further add the composition of following composition, mix, thereby modulate cured composition for color R3 of the present invention (colored resist liquid).In addition, the pigment concentration in the total solid composition of the cured composition for color R3 of gained is 48%.

(composition)

30 parts of the exemplary compounds A-1 of record in the above-mentioned table 1

(the system A-BPE-4 of Xin Zhong village chemical industrial company, specific 2 functional monomers)

2-(Chloro-O-Phenyl)-4,13 parts of 5-diphenyl-imidazole dipolymers

(Photoepolymerizationinitiater initiater)

6 parts of 4,4 '-two (lignocaine) benzophenone (sensitizing coloring matter)

6 parts of 2-mercaptobenzothiazoles (giving the hydrogen compound)

230 parts of propylene glycol methyl ether acetates

In addition, the pigment concentration among the cured composition for color R3 calculates according to as described below.

Pigment (PG36+PY150+ phthalocyanine derivates)=110 parts

Solid constituent=pigment (110 parts)+benzyl methacrylate/methacrylic acid copolymer (75 * 0.4=30 part)+spreading agent (35 parts)+55 parts (specific 2 functional monomers+Photoepolymerizationinitiater initiater+sensitizing coloring matter+to the hydrogen compound)=230 parts

Pigment concentration=110/230 * 100=48%

(comparative example 4)

The preparation of＜viridine green dispersive composition 〉

The composition of following composition is mixed, stir with rotating speed 3000r.p.m. with homogenizer and mixed in 3 hours, preparation contains the mixed solution of pigment.

(composition)

70 parts of pigment green 36s (average primary particle diameter is 25nm)

30 parts of pigment yellows 150 (average primary particle diameter is 25nm)

10 parts of phthalocyanine derivates

(SOLSPERSE 3000, ア PVC シ ア (Avecia) Co., Ltd. system)

75 parts of the propylene glycol methyl ether acetate solution (solid constituent 40%) of benzyl methacrylate/methacrylic acid (=70/30[mol ratio]) multipolymer (Mw is 5,000)

35 parts of spreading agents (BYK-161, BYK corporate system)

495 parts of propylene glycol methyl ether acetates

Then, further the bead dispersion machine (GETZMANN corporate system) of the zirconium dioxide pearl by having used 0.3mm φ carries out 6 hours dispersion treatment to the above-mentioned mixed solution that obtains.Further use the high pressure dispersion machine NANO-3000-10 that has the mechanism of decompressor (Japanese BEE Co., Ltd. system) then, at 2000kg/cm ³Pressure under, carry out dispersion treatment with 500g/ minute flow.Repeat this dispersion treatment 10 times, obtain the viridine green dispersive composition.

In the viridine green dispersive composition that obtains, further add the composition of following composition, mix, thereby modulate cured composition for color R4 of the present invention (colored resist liquid).In addition, the pigment concentration in the total solid composition of the cured composition for color R4 of gained is 48%.

(composition)

30 parts of tetramethylol methane tetraacrylate

(the system A-TMMT of Xin Zhong village chemical industrial company, 4 functional acrylates)

2-(Chloro-O-Phenyl)-4,10 parts of 5-diphenyl-imidazole dipolymers

(Photoepolymerizationinitiater initiater)

5 parts of 4,4 '-two (lignocaine) benzophenone (sensitizing coloring matter)

5 parts of 2-mercaptobenzothiazoles (giving the hydrogen compound)

EHPE-3150 (Daicel chemical company system) (thermal cross-linking agent) 5 parts

230 parts of propylene glycol methyl ether acetates

In addition, the pigment concentration among the cured composition for color R4 calculates according to as described below.

Pigment (PG36+PY150+ phthalocyanine derivates)=110 parts

Solid constituent=pigment (110 parts)+benzyl methacrylate/methacrylic acid copolymer (75 * 0.4=30 part)+spreading agent (35 parts)+55 parts (4 functional monomers+Photoepolymerizationinitiater initiater+sensitizing coloring matter+to hydrogen compound+thermal cross-linking agent)=230 parts

Pigment concentration=110/230 * 100=48%

(comparative example 5)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to relatively using the monomer C-1 of putting down in writing in the following table 2, all carry out similarly to Example 1, make obtaining cured composition for color R5.

(comparative example 6)

Except specific 2 functional monomers that will use among the embodiment 1 are that exemplary compounds A-1 replaces to relatively using the monomer C-2 of putting down in writing in the following table 2, all carry out similarly to Example 1, make obtaining cured composition for color R6.

The formation of＜cured composition for color layer 〉

-coating-

According to following condition the above-mentioned cured composition for color slot coated that obtains is arrived on the glass substrate of 550mm * 650mm.Then, implement vacuum drying and prebake conditions (100 ℃ 80 seconds), form the cured composition for color layer.

(slot coated condition)

The gap of the peristome of dispense tip front end: 50 μ m

Coating speed: 100mm/ second

The space of substrate and dispense tip: 150 μ m

Coating thickness (dry film thickness): 2.0 μ m

Coating temperature: 23 ℃

-expose, develop-

Then, with 20mW/cm ²The ultrahigh pressure mercury lamp of energy as light source, (wide 20 μ m) shine 50mJ/cm to the cured composition for color layer with pattern-like via mask ²Exposure, after the exposure, be that 1.0% aqueous solution of developer solution (trade name: CDK-1, FILM Electronic Materials Co., Ltd. of Fuji system) sprays development to the whole face of cured composition for color layer with KOH, wash with pure water.

The cured composition for color layer that the enforcement development treatment is obtained heats 0.5 hour (back baking) in 230 ℃ baking oven.Thus, on glass substrate, form colored pattern, obtain color filter.

-estimate-

Live width, cross sectional shape, film strength and ITO sputter adaptability to the colored pattern that forms on glass substrate are estimated according to following, and the result is as shown in table 3 is summed up.

The live width of＜colored pattern 〉

The live width of the colored pattern after mensuration exposure, development and the heat treated (back baking).

Zero: it is above and less than the high meticulous colored pattern of 21 μ m to obtain width and be 19 μ m.

*: width is more than the 21 μ m and can't obtains high meticulous colored pattern.

The cross sectional shape of＜colored pattern 〉

By field emission type scanning electron microscope S-4800 (HITACHI corporate system) cross sectional shape of the colored pattern of formation is observed, and estimated.

Zero: coning angle is more than 30 degree and less than 85 scopes of spending (positive taper)

*: coning angle is 85 degree above (rectangle or back taper)

The film strength of＜colored pattern, ITO sputter adaptability 〉

The small hardness of the colored pattern of formation is estimated according to following standard by nano hardness meter (Nanoindenter SA2, MTS SYSTEM corporate system).

Zero: colored pattern hardness (H) is more than the 0.25GPa, has sufficient pattern hardness.

*: colored pattern hardness (H) is less than 0.25GPa, pattern hardness deficiency.

In addition, be formed with on the color filter of colored pattern, using MH90-1117 (ULVAC corporate system) sputtering ITO transparency electrode.

Under colored pattern hardness (H) is situation more than the 0.25GPa, form after the ito transparent electrode by sputter, at this colored pattern surface observation less than wrinkle.But under the situation of pattern hardness (H), form after the ito transparent electrode by sputter less than 0.25GPa, at this colored pattern surface observation to wrinkle.Thus, can infer that in the liquid crystal display cells that has used this color filter, the demonstration that liquid crystal can take place is bad.

Table 3

	Cured composition for color	Live width	Pattern form	ITO sputter adaptability (pattern hardness)
					Embodiment 1	1	○	○	○
Embodiment 2	2	○	○	○
					Embodiment 3	3	○	○	○
Embodiment 4	4	○	○	○
					Embodiment 5	5	○	○	○
Embodiment 6	6	○	○	○
					Embodiment 7	7	○	○	○
Embodiment 8	8	○	○	○
					Comparative example 1	R1	×	○	○
Comparative example 2	R2	○	×	○
					Comparative example 3	R3	○	○	×
Comparative example 4	R4	○	×	○
					Comparative example 5	R5	○	×	×
Comparative example 6	R6	○	×	○

From the result of table 3 as can be seen, use the live width of the colored pattern that the cured composition for color of embodiment forms little, the cross sectional shape of colored pattern is good, and film strength is also high.

Claims (8)

1, a kind of cured composition for color, it contains (a) and have the polymerizable monomer of 2 ethylenic unsaturated links or oligomer, (b) Photoepolymerizationinitiater initiater, (c) thermal cross-linking agent and (d) colorant in molecule; Described (a) has 2 ethylenic unsaturated links in molecule polymerizable monomer or oligomer are that the I/O value is below 0.65, and the distance between the intramolecular ethylenic unsaturated link is 60 below the atom, and have the ring structure more than 2 in molecule; And the content of described (d) colorant is more than the 30 quality % and below the 60 quality % with respect to the total solid composition of cured composition for color.

2, cured composition for color according to claim 1, wherein, the softening point of described (c) thermal cross-linking agent is more than-100 ℃ and below 130 ℃.

3, cured composition for color according to claim 1, wherein, described (c) thermal cross-linking agent has the ring structure more than 1 in molecule.

4, cured composition for color according to claim 1, wherein, the heat cross-linking group equivalent of described (c) thermal cross-linking agent is more than 50 and below 1000.

5, cured composition for color according to claim 1, it is used to form the colored pattern in the color filter.

6, a kind of color filter, it has the colored pattern that uses each the described cured composition for color in the claim 1～5 to form on substrate.

7, a kind of manufacturing method of color filter, it comprises following step: on substrate, use in the claim 1～5 each described cured composition for color by be coated with repeatedly, prebake conditions, exposure, development and heat treated form colored pattern arbitrarily.

8, a kind of liquid crystal indicator, it is equipped with the described color filter of claim 6.