DESCRIPTION

PIGMENTS, AS WELL AS PIGMENT DISPERSIONS, COLORED

COMPOSITIONS AND COLOR FILTERS USING THEM

TECHNICAL FIELD

[0001] The present invention relates to pigments, compounds constituting the pigments, as well as pigment dispersions, colored compositions, curable colored compositions, color resist solutions, color filters, inks for inkjet printing and processes for preparing

radiation-sensitive colored compositions using them.

BACKGROUND ART

[0002] Conventionally, colorants capable of efficiently transmitting wavelengths of bright lines from backlight sources to display color images with high luminance have been advantageously employed as color materials for color filters used in small liquid crystal display devices and organic EL display devices for mobile phones, mobile video game consoles, PDAs and the like because these display devices necessarily required the use of backlight sources powered by secondary batteries or dry batteries or the like with limited electric capacity.

Recently, liquid crystal display device and organic EL display device have become increasingly larger for uses in display monitors of personal computers, television receivers and the like, and weight is attached to color reproducibility in these display devices. Weight is also attached to heat resistance and volatility for outdoor uses.

[0003] As for colorants used for color filters, patent document 1 proposes colorants comprising a metal chelate dye of a symmetric methine dye having a specific structure, while patent document 2 proposes colorants consisting of a mixture of any one of a symmetric methine dye, a polymethine dye, and a squarylium dye of a specific structure with a metal ion-containing compound, for example. Further, patent document 3 proposes metal complex dyes formed from a methine dye or an azomethine dye with a metal, while patent document 4 proposes colorants comprising a dye of a specific structure, for example.

REFERENCES

PATENT DOCUMENTS

[0004 ] Patent document 1: JP-A2007 - 100061

Patent document 2: JP-A2001 - 34236

Patent document 3: JP-A-H 9- 143382

Patent document : JP-A2005 -250420

DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] However, our studies revealed that the dye described in patent document 1 is insufficient in heat resistance, volatility and solvent resistance because the methine dye exists as a neutral ligand. Further, the dye having the structure described in patent document 2 or 3 was found to be poor in heat resistance and the like. The present

■ invention was accomplished to overcome these disadvantages, and aims to provide pigments having excellent heat resistance and volatility, compounds constituting the pigments-, as well ^' as pigment compositions, colored

■ compositions, curable colored compositions, color filters, inks for inkjet printing, and processes for preparing .radiation-sensitive colored compositions using them.

. MEANS FOR SOLVING THE PROBLEMS

[0006] As a result of careful studies to solve the problems described above, we found that these problems can be solved by using a. pigment comprising a metal complex of a methine dye having a specific structure.

The means for solving the problems described above is shown as <1> below, preferably <2> to <20> below.

<1> A igment represented by formula (I):

Formula ( I ) ; in formula (I) , R ¹ to R ⁴ each independently represent alkyl, aryl, heterocyclyl , alkoxycarbonyl , carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R ⁵ represents a hydrogen atom, alkyl, aryl or heterocycly1 ; M represents a monovalent to trivalent metal; and L represents an anion or a ligand capable of coordinating with the metal; m represents an integer of 1 to 3; and n represents an integer of 0 to 2; the group included in the parentheses forms a monovalent anion as the entire group.

<2> The pigment according to <1>, wherein R ³ and R ⁴ each represent an alkyl group containing 1 to 5 carbon atoms in formula (I) above.

<3> The pigment according to <1> or <2>, wherein R ¹ and R ² each independently represent alkyl, aryl or heterocyclyl in formula (I) above.

<4> The pigment according to any one of <1> to <3>, wherein, in formula (I) above, R ¹ and R ² are the same group, and R ³ and R ⁴ are the same group.

<5> The pigment according to any one of <1> to <4>, which has a resistance to solvent bleeding of grade 5 as evaluated by absolute comparison according to JIS K 5101-1991 15.

<6> The pigment according to any one of <1> to <5>, wherein n is 0 in formula (I) above.

<7> The pigment according to any one of <1> to <6>, wherein the compound represented by formula (I) above is a compound

Formula (I-A) ;

in formula (I-A) , R ¹ to R ⁴ each independently represent alkyl, aryl, heterocyclyl, alkoxycarbonyl, carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R ⁵ each independently represents a hydrogen atom, alkyl, aryl or heterocyclyl ; and M' represents a divalent metal atom; the groups included in the parentheses each form a monovalent anion as the entire group .

<8> The pigment according to any one of <1> to <7>, wherein M in formula (I) above and M' in formula (I-A) above represent zinc.

<9> The pigment according to any one of <1> to <8>, wherein the compound represented by formula (I) above is any one of the compounds represented by formulae (I-a) to (I-n) below :

in (I-f) and (1-1), Me represents methyl.

<10> The pigment according to any one of <1> to <9>, wherein the compound represented by formula (I) above has a molecular weight of 500 to 1200.

<11> A pigment dispersion comprising at least one pigment according to any one of <1> to <10>.

<12> A colored composition comprising at least one pigment according to any one of <1> to 10.

<13> A curable colored composition comprising at least one pigment according to any one of <1> to <10>.

<14> A radiation-sensitive colored composition comprising at least one pigment according to any one of <1> to <10>.

<15> A color filter formed by using the curable colored composition according to <13>.

<16> An ink for inkjet printing using the colored composition according to <12>.

<17> A solid-state image sensor or a liquid crystal display device comprising the color filter according to <15>. <18> A process for preparing a color filter, comprising applying the curable colored composition according to claim 13 on a substrate; exposing the applied curable colored composition in a pattern through a mask; and developing the curable colored composition exposed in a pattern with an alkaline developer.

[0007]

<19> A composition comprising a compound represented by ^■ formula (I) , characterized in that the compound represented by formula (I) accounts for 50 % by mass or more in the composition:

Formula (I)

in formula (I) , R ¹ to R ⁴ each independently represent alkyl, aryl, heterocyclyl , alkoxycarbonyl, carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R ⁵ represents a hydrogen atom, alkyl, aryl or heterocyclyl ; M represents a monovalent to trivalent metal; and L represents an anion or a ligand capable of coordinating with the metal; m represents an integer of 1 to 3; and n represents an integer of 0 to 2; the group included in the parentheses forms a monovalent anion as the entire group .

<20> The composition according to <19>, wherein the compound represented by formula ^' (I) above is a compound represented

Formula ( I-A) ;

in formula (I-A) , R ¹ to R ⁴ each independently represent alkyl, aryl, heterocyclyl, alkoxycarbonyl, carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R ⁵ each independently represents a hydrogen atom, alkyl, aryl or heterocyclyl; and M' represents a ^' divalent metal atom; the groups included in the parentheses each form a monovalent anion as the entire group.

ADVANTAGES OF THE INVENTION

[0008] According to the present invention, pigments having excellent heat resistance and volatility, compounds constituting the pigments, as well as pigment compositions, colored compositions, curable colored compositions, color filters, inks for inkjet printing, and processes for preparing radiation-sensitive colored compositions using them can be provided.

THE BEST MODES FOR CARRYING OUT THE INVENTION

[0009] The present invention will be explained in detail below. As used herein, the numerical ranges expressed with "to" means the ranges including the values indicated before and after "to" as lower and upper limits. Also as used herein, the term "organic EL device" refers to an organic electroluminescent device.

As used herein, the term "radiation" means to include visible rays, ultraviolet rays, far-ultraviolet rays, electron beams, X rays and the like. Also as used herein, the term "colored layer" refers to a layer composed of a pixel and/or a black matrix used in color filters.

Further, the term "pigment" as used herein refers to a compound slightly soluble in water and organic solvents, preferably a compound having a resistance to solvent bleeding of grade 4 or grade 5, more preferably grade 5 or higher as evaluated by absolute comparison according to JIS K 5101-1991 15. More specifically, it refers to a compound evaluated as grade 5 according to the standard described in Handbook of Organic Pigments edited by Color Office, page 363.

[0010] (Pigments)

The pigments of the present invention are characterized in that they are represented by formula (I) . The present invention also provides compositions comprising a compound represented by formula (I), characterized in that the compound represented by formula (I) accounts for 50 % by mass or more, or even 80 % by mass of colorants in the compo s it ions .

Formula (I)

In formula (I) , R ¹ to R ⁴ each independently represent alkyl, aryl, heterocyclyl , al koxycarbonyl , carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R ⁵ represents a hydrogen atom, alkyl, aryl, or heterocyclyl ; M represents a monovalent to trivalent metal; and L represents an anion or a ligand capable of coordinating with the metal. m represents an integer of 1 to 3; and n represents an integer of 0 to 2. The" group included in the parentheses forms a monovalent anion as the entire group.

[0011] R ¹ to R ⁴ each independently represent alkyl, aryl, heterocycly1 , alkoxycarbonyl , carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano.

Preferably, the alkyl is each an alkyl group containing 1 to 20 carbon atoms, more preferably an alkyl group containing 1 to 10 carbon atoms, especially preferably an alkyl group containing 1 to 5 carbon atoms. The alkyl group may be straight-chain or branched-cha in or cyclic, and may be further substituted. Specific examples of alkyl groups include methyl , ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl,

tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl , 2 -methylhexy1 , cyclohexyl, cyclopentyl, 2-norbornyl and the like, among which methyl, ethyl, propyl, butyl, pentyl, isopropyl and tert-butyl are preferred, more preferably methyl.

Substituents that may be present on the alkyl group include alkoxy groups containing 1 to 10 carbon atoms, thioalkoxy groups containing 1 to 10 carbon atoms, cyano, amino, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like.

[0012] Preferably, the aryl is an aryl group containing 6 to 30 carbon atoms, more preferably an aryl group containing 6 to 14 carbon atom, especially preferably an aryl group containing 6 to 10 carbon atoms. The aryl group may be further substituted. Specific examples of aryl groups include phenyl , p-methylphenyl , naphthyl, anthranyl and the like. Substituents that may be present on the aryl group are the same as the substituents that may be present on the alkyl group. Among others, phenyl, p-methoxypheny1 , o-methoxyphenyl , p-chlorophenyl , and o-chloropheny1 are preferred, more preferably p-methoxypheny1 ,

o-methoxyphenyl, p-chlorophenyl, and o-chloropheny1.

[0013] Preferably, the heterocyclyl is a heterocyclyl group containing ^' 6 to 30 carbon atoms, more preferably a heterocyclyl group containing 6 to 14 carbon atoms, especially preferably a heterocyclyl group containing 6 to 10 carbon atoms. The heterocyclyl group may be further substituted. Specific examples of heterocyclyl groups include pyrrole , pyrazole, imidazole, pyridine, pyrimidine, furan, thi phene, oxazole, thiazole as well as benzo-fused ring systems and heterocyclic fused ring systems thereof and the like, among which pyrrole, pyrazole, imidazole, pyridine and pyrimidine are preferred, more preferably pyridine .

[0014] Preferably, the a.lkoxycarbonyl is an alkoxycarbonyl group containing 1 to 30 carbon atoms, more preferably an alkoxycarbonyl group containing 1 to 10 carbon atoms, especially preferably an alkoxycarbonyl group containing 1 to 6 carbon atoms. The alkoxycarbonyl group may be straight-chain or branched-chain or cyclic, and may be further substituted. Specific examples of alkoxycarbonyl groups include methoxycarbonyl , ethoxycarbony1 ,

tert-butoxycarbonyl , n-octadecyloxycarbonyl and the like, among which methoxycarbonyl and tert-butoxycarbonyl are preferred. Substituents that may be present on the alkoxycarbonyl group are the same as the substituents that may be present on the alkyl group.

[0015] Preferably, the carbamoyl is a carbamoyl group containing 0 to 30 carbon atoms, more preferably a carbamoyl group containing 0 to 10 carbon atoms, especially preferably a carbamoyl group containing 0 to 6 carbon atoms. The carbamoyl group may be straight-chain or branched-cha in or cyclic, and may be further substituted. Specific examples of carbamoyl groups include carbamoyl, N-methyl carbamoyl , N, -dimethylcarbamoyl , N, N-di-n-octylcarbamoy1 ,

N- (methylsulfonyl ) carbamoyl and the like, among which carbamoyl and N-methylcarbamoyl are preferred.

Substituents that may be present on the carbamoyl group are the same as the substituents that may be present on the alkyl group .

[0016] Preferably, the alkoxy is each an alkoxy group containing 1 to 20 carbon atoms, more preferably an alkoxy group containing 1 to 10 carbon atoms, especially preferably an alkoxy group containing 1 to 3 carbon atoms. The alkoxy group may be straight-chain or branched-chain or cyclic, and may be further substituted . Specific examples of alkoxy g ^' roups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy and the like, among which methoxy and ethoxy are preferred. Substituents that may be present on the alkoxy group are the same as the substituents that may be present on the alkyl group.

The amino may be substituted or preferably unsubst ituted . Examples of groups forming a sulfonamide, a sulfonic acid ester or a sulfone include alkoxysulfonyl groups

(preferably al koxysul fony1 groups containing 1 to 3 carbon atoms), aryloxysul fony1 groups (preferably aryloxysulfonyl groups containing 6 to 8 carbon atoms) , alkylsulfonyl groups (preferably alkylsulfonyl groups containing 1 to 3 carbon atoms), arylsulfonyl groups (preferably arylsulfonyl groups containing 6 to 8 carbon atoms), and aminosul fonyl groups optionally substituted by an alkyl or aryl group on the nitrogen atom (preferably aminosulfonyl groups optionally substituted by an alkyl group containing 1 to 3 carbon atoms or an aryl group containing 6 to 8 carbon atoms on the nitrogen atom) .

[0017] Among them, R ¹ and R ² are each preferably alkyl, aryl or heterocyclyl , more preferably aryl or het erocyclyl . More specifically, methyl, p-methoxypheny 1 ,

o-methoxyphenyl , p-chlorophenyl , o-chlorophenyl and pyridine are preferred.

R ³ and R ⁴ are each preferably alkyl, aryl or heterocyclyl, more preferably alkyl, more preferably an alkyl group containing 1 to 5 carbon atoms , still more preferably methyl . R ³ and R ⁴ are preferably the same group, and more preferably R ¹ and R ² are also the same group. The symmetric compound represented by formula (I) has the advantages that the desired absorption characteristics (bluish tint) can be obtained and that it can be readily prepared. It also has the advantage that association is improved, whereby it can be readily converted into a pigment.

[0018] R ⁵ each independently represents a hydrogen atom, alkyl, aryl or heterocyclyl. The alkyl, aryl and

heterocyclyl represented by R ⁵ have the same meanings as defined. for the alkyl, aryl and heterocyclyl- represented by R ¹ to R ⁴ , and also cover similar preferred ranges.

Preferably, R ⁵ is a hydrogen atom or alkyl, more preferably a hydrogen atom.

[0019] M represents a monovalent to trivalent metal. Examples of monovalent to trivalent metals include Li, Na, K, Cs, Be, Mg, Ca, Ba, Zn, Cd, Al, Ga, In, Yb, B and the like. Among them, Zn is preferred.

[0020] L represents an anion or a ligand capable of coordinating with the metal . The ligand is not specifically limited so far as it can coordinate with M in formula (I) , but it preferably has a substituent containing C, N, 0 or S, still more preferably has a group containing a lone pair of electrons such as N, 0 or S. Compounds forming the ligand include those having carboxylate , carbonyl (ester, ketone) , phosphate, sulfonate, amine, amide, sulfonamide, urethane, urea, alcohol, thiol or the like, preferably those having carboxylate, carbonyl (ester, ketone) , phosphate,

sulfonate or amine, still more preferably those having carboxylate, carbonyl (ester, ketone), phosphate or amine. The number of the coordinating groups contained in the molecule is not limited to only one, but two or more of them may be contained and they may or may not dissociate.

Examples of anions capable of coordinating with the metal include halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom), C10 ₄ , S0 ₄ , CN, SCN, BF ₄ , PF6, and BPh ₄ wherein Ph represents phenyl.

[0021] m represents an integer of 1 to 3, preferably 1 to 2, more preferably 2.

n represents an integer of 0 to 2, preferably 0 to 1, more preferably 0.

[0022] Formula (I) forms a monovalent anion as the entire group included in the parentheses. Primarily, six nitrogen atoms together form a monovalent anion, but carbon atoms or substituents or the like may contribute to the formation of the anion. In other words, formula (I) has a structure forming a coordinate bond and/or an ionic bond between the group included in the parentheses and M (a monovalent to trivalent metal) .

[0023] Preferably, the compound represented by formula (I) is a compound represented by formula (I-A) .

Formula (I-A)

In formula (I-A) , R ¹ to R ⁴ each independently represent alkyl, aryl, heterocyclyl , alkoxycarbonyl , carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R ⁵ each independently represents a hydrogen atom, alkyl, aryl or heterocyclyl ; and M' represents a divalent metal atom. The groups included in the parentheses each form a monovalent anion as the entire group. [0024] In formula (I-A), R ¹ to R ⁴ have the same meanings as defined for R ¹ to R ⁴ in formula (I) , and also cover similar preferred ranges.

In formula (I-A), R ⁵ has the same meaning as defined for R ⁵ in formula (I), and also covers similar preferred ranges.

[0025] M' represents a divalent metal. Examples of divalent metals include Be, Mg, Ca, Ba, Zn, Cd and the like. Among them, Zn is preferred.

[0026] Preferably, the compound represented by formula (I) has a molecular weight of 500 to 1200, more preferably 500 to 1000, still more preferably 500 to 900. When the molecular mass is 500 to 1200, hue and volatility tend to improve.

[0027] Preferably, the mass of each of R ³ and R ⁴ moieties per molecule of the compound represented by formula (I) is 2 to 200, more preferably 2 to 150, especially preferably 12 to 80. Such a structure tends to provide a compound with higher purity.

[0028] Specific examples of compounds represented by formula (I) are shown below. In the formulae below, Me represents methyl. Compounds of the formulae below wherein Zn is replaced by Be, Mg, Ca, Ba or Cd can also preferably be employed as compounds of the present invention.

( I -m) ( I— n )

[0029] Among the compounds represented by (I-a) to (I-n), those represented by (I-a) to (1-1) are preferred.

[0030] The compound represented by formula (I) can be synthesized on the basis of known methods. For example, exemplary compound (I-a) can be synthesized according to the scheme shown below.

[0031] As shown in the scheme above, the compound represented by formula (I) can be synthesized.

[0032] Preferably, the pigments, of the present invention comprise a compound represented by formula (I) having a resistance to solvent bleeding of grade 5 as evaluated by absolute comparison according to JIS K 5101-1991 15.

Preferably, the compound represented by formula (I) has a hue expressed as Amax of 420 to 470, more preferably Xmax of 430 to 465, still more preferably Xmax of 440 to 460.

[0033] Preferably, the colored compositions of the present invention comprise a colorant containing the compound represented by formula (I) as a major component. The term "major component" refers to a component incorporated at the highest content among blue colorants incorporated.

Examples of colored compositions in the present invention include radiat ion- sens it ive colored compositions used for color resist solutions and the like and inks for inkjet printing .

[0034] Methods for converting the compounds of the present invention into pigments include removing soluble groups, introducing a hydrogen-bonding group into the molecule to increase intramolecular and int ermolecular hydrogen bonding strength, introducing a substituent for n-electron systems or the like to increase intermolecular n-n stacking strength and the like. Further, other available methods for converting them into pigments include polymerizing them, strengthening intermolecular interactions by halogen interactions and the like.

Soluble groups include long chain alkyl and alkenyl groups containing six or more carbon atoms and the like. Hydrogen-bonding groups include, for example, hydroxyl, thiol, alkoxy, thioalkoxy, amino, carbamate, amide, sulfonamide, ureido, thioureido, phosphate and the like. Substituents for n-electron systems include substituents containing unsaturated bonds, substituted and

unsubst ituted aryl groups, aromatic heterocyclyl groups and the like.

[0035] (Pigment dispersions)

The pigment dispersions of the present invention are characterized in that they comprise at least one of the pigments described above. This allows the pigment dispersions to be provided with excellent dispersion stability, coloring power, and light resistance.

[0036] The pigment dispersions of the present invention may be aqueous or non-aqueous. Preferably, they are

dispersions in solvents.

[0037] The solvents include, for example, aromatic solvents such as toluene, xylene and methoxybenzene ;

acetate ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethyl 3-ethoxypropionate ; alcohol solvents such as methanol and ethanol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as

N , -dimethyl formamide , γ-butyrolactam,

N-methyl-2-pyrrolidone, aniline and pyridine; lactone solvents such as γ-butyrolactone ; carbamate ester solvents such as a 48:52 mixture of methyl carbamate and ethyl carbamate and the like.

[0038] The pigments of the present invention may be used as mixtures with other colorants. In this case, the other colorants may be pigments or dyes. For example, a preferred embodiment may include a green colorant (e.g., for use in green color filters) formed by mixing a pigment having a phthalocyanine skeleton of blue hue and a pigment of the present invention in an appropriate ratio.

[0039] Also a surfactant or dispersant may be used in order to further improve dispersibility of the pigment and image quality.

[0040] <Surfactant>

The surfactant usable herein includes various surfactants such as fluorine-containing surfactant, nonionic

surfactant, cationic surfactant, anionic surfactant, silicone-based surfactant.

[0041] Examples of the fluorine-containing surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781 (all from DIC Corporation) , Fluorad FC 30 , FC431, FC171 (all from Sumitomo 3M Ltd.), Surflon S-382, SC-101, SC-103,

SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all from Asahi Glass Co . Ltd.), andPF636, PF656, PF6320, PF6520, PF7002 (from OMNOVA Solutions Inc.) .

Fluorine content in the fluorine-containing surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly 7% by mass to 25% by mass.

[0042] Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, pol yoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether,

oxyet hylene-oxypropylene block copolymer,

t-oct ylphenoxye thyl polyethoxyethanol , nonylphenoxyethy1 polyethoxyethanol , glycerol, trimethylol propane,

trimethylol ethane as well as ethoxylate and propoxylate thereof (for example, glycerol propoxylate, glycerin ethoxylate, ^' etc.), polyoxyethylene lauryl ether,

polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, and Tet ronic 304 , 701, 704, 901, 904, 150R1, all from BASF GmbH), and Solsperse 20000 (from The Lubrizol Corporation) .

[0043] Specific examples of the cationic surfactant include t etraal kylammonium salt, alkylamine salt,

benzalkonium salt, alkyl pyridinium salt, and imidazolium salt. Specific examples include

dihydroxyethylstearylamine,

2 -hept adeceny1 -hydro ye t hyl imida zo 1 ine , laur y 1

dimethylbenzylammonium chloride, cetylpyr idinium chloride, and stearamide methylpyr idinium chloride. More specific examples include phthalocyanine derivative (EFKA-745, from Morishita & Co. Ltd. ) , organosiloxane polymer KP341 (from Shin-Etsu Chemical Co. Ltd.) , (meth ) aery late-based

(co) polymer Polyflow No.75, No.90, No.95 (from Kyoeisha Chemical Co. Ltd. ) , and W001 (from Yusho Co. Ltd.) .

[ 0044 ] Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium lauryl sul f ona t e , sodium alkyl diphenyl ether disulfonate, sodium

alkylnaphthalene sulfonate, sodium dialkylsulf osuccinate , sodium stearate, potassium oleate, sodium

dioctylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfonate, sodium dialkylsulfosuccinate, sodium stearate, sodium oleate , and t-octyl phenoxyet hoxy polyethoxyethyl sulfate, from which a single species, or two or more species are selectable. Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether,

polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenylether, oxyethy lene-oxypropylene block copolymer, t-octyl phenoxy ethyl polyethoxyethanol, and nonyl phenoxyethyl polyethoxyethanol, from which a single species, or two or more species are selectable. Specific examples include W004, W005, and W017 (from Yusho Co. Ltd. ) .

[0045] Examples of the silicone-based surfactant include Toray Silicone DC 3 PA, SH7PA, DCllPA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (all from Dow Corning Toray Co., Ltd. ) , TSF-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (all from Momentive Performance Materials Inc.) , KP341, KF6001 and KF6002 (all from Shin-Etsu Chemical Co., Ltd.) ^' , arid BYK307, BYK323 and BYK330 (all from BYK-Chemie) .

The surfactant may be used independently, or two or more species of which may be combined.

[0046] For the case where the water-based pigment

dispersion in the present invention contains the surfactant, the content of which is not specifically limited. The content may be, for example, 0 to 100% by mass of the pigment.

[0047] <Dispersants>

Dispersants that can be used in the present invention include polymeric dispersants [for example, polyamidoamines and their salts, polycarboxylic acids and their salts, high-molecular weight unsaturated acid esters, modified polyurethanes , modified polyesters, modified

poly (meth ) acrylates , (meth) acrylic copolymers, and

naphthalenesulfonic acid / formaldehyde condensates];

surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and alkanolamines ; and pigment derivatives, etc.

Polymeric dispersants can be further classified by their structure into straight chain polymer s , terminally modified polymers, graft polymers, and block polymers.

[0048] Terminally modified polymers having an anchoring moiety for pigment surfaces include, for example, the polymers having a terminal phosphate group described in JP-A-H3-112992, JP-A2003- 533455 and the like; the polymers having a terminal sulfonate group described in

JP-A2002-273191 and the. like; and the polymers having a partial skeleton or heterocycle of an organic dye described in JP-A-H9-77994 and the like; etc. Further, the polymers containing two or more terminal anchoring moieties for pigment surfaces (acid groups, basic groups, partial skeletons or heterocycles of organic dyes and the like) described in JP-A2007-277514 are also preferred because of excellent dispersion stability.

[0049] Graft polymers having an anchoring moiety for pigment surfaces include, for example, the reaction products of a poly (lower alkylene imine) and a polyester described in JP-A-S54-37082 , JP-A-H8-507960 , JP-A2009-258668 and the like; the reaction products of a polyallylamine and a polyester described in JP-A-H9-169821 and the like; the copolymers of a macromonomer and a nitrogen-containing monomer described in JP-A-H10 - 339949 , JP-A2004-37986 and the like; the graft polymers having a partial skeleton or heterocycle of an organic dye described in JP-A2003-238837, JP-A2008 - 9 26 , JP-A2008 - 81732 and the like; the copolymers of a macromonomer and an acid group-containing monomer described in JP-A2010 - 106268 and the like; etc. Among others, the amphoteric dispersant resins having a basic group and an acidic group described in JP-A2009-203462 are especially preferred because of the dispersibility and dispersion stability of the resulting pigment dispersions and the developability shown by curable colored compositions using such pigment dispersions.

[0050] Macromonomer s that can be used for preparing graft polymers having an anchoring moiety for pigment surfaces by radical polymerization include known macromonomer s such as macromonomers AA-6 (methyl polymethacrylate having a terminal methacryloyl group) , AS-6 (polystyrene having a terminal methacryloyl group) , AN-6S (a

styrene-acrylonitrile copolymer having a terminal methacryloyl group) , and AB-6 (butyl polyacrylate having a terminal methacryloyl group) available from Toagosei Co. , Ltd.; PLACCELs FM5 (an adduct of 2 -hydr oxyethy 1

methacrylate with 5 molar equivalents of ε -caprolact one ) , and FA10L (an adduct of 2 -hydroxyet hy1 acrylate with 10 molar equivalents of ε -caprolactone ) available from Daicel Chemical Industries, Ltd. ; and the polyester macromonomers described in JP-A-H2 -272009 and the like. Among them, polyester macromonomers having high flexibility and affinity for solvents are especially preferred because of the dispersibility and dispersion stability of the resulting pigment dispersions and the developability shown by curable colored compositions using such pigment dispersions, among which those represented by the polyester macromonomers described in JP-A-H2 -272009 are most preferred .

[0051] Preferred block polymers having an anchoring moiety for pigment surfaces include the block polymers described in JP-A2003-49110, . JP-A2009 - 52010 and the like.

[0052] Pigment dispersants that can be used in the present invention are also commercially available, specific examples of which include " Di sperby k- 101 (polyamidoamine phosphate) , 107 (carboxylic acid ester) , 110 (an acid group-containing copolyme ) , 130 (polyamide) , 161, 162, 163, 164, 165, 166, 170 (high molecular weight copolymers )" , and "BYK-P104, P105 (high-molecular weight unsaturated polycarboxylic acids)" available from BYK Chemie; "EFKA 4047, 4050 to 4010 to 4165 (polyurethane polymers) , EFKA 4330 to 4340 (block copolymers) , 4400 to 4402 (modified polyacrylates ) , 5010 (polyester amide) , 5765

(high-molecular weight polycarboxylic acid salt) , 6220 (fatty acid polyester) , 6745 (phthalocyanine derivative) , 6750 (azo pigment derivative) " available from EFKA;

"AJISPER PB821, PB822, PB880, PB881" available from

Ajinomoto Fine-Techno Co., Inc. ; "FLOWLEN TG-710 (urethane oligomer)", and "POLYFLOW No. 50E, No. 300 (acrylic copolymers)" available from Kyoeisha Chemical Co., Ltd. ; "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic

polycarboxylic acids) , #7004 (polyether ester) , DA-703-50, DA-705, DA-725" available from Kusumoto Chemicals, Ltd.; " DEMOL RN, N ( naphtha 1 ene sul foni c acid / formaldehyde polycondensates ) , MS, C, SN-B (aromatic sulfonic acid / formaldehyde polycondensates)", "HOMOGENOL L-18

(polycarboxylate polymer)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ethers)", and "ACETAMIN 86 ( s tearylamine acetate)" available from Kao Corporation; "Solsperse 5000 (phthalocyanine derivative) , 22000 (azo pigment derivative) , 13240 (polyester amine) , 3000, 17000, 27000 (terminally funct ionali zed polymers ) , 24000, 28000, 32000, 385.00 (graft polymers)" available from Lubrizol Japan Limited; "Nikkol T106 (polyoxyethylene sorbitan monooleate) , and MYS-IEX (polyoxyethylene monostearate) " available from Nikko Chemicals Co. , Ltd. ; Hinoact T-8000E and the like available from Kawaken Fine Chemicals, Co. , Ltd.; the organosiloxane polymer KP341 available from Shin-Etsu Chemical Co., Ltd.; cationic surfactants such as "W001", nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether,

polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate and sorbitan fatty acid ester, and anionic surfactants such as "W004, W005, 017" available from Yusho Co., Ltd.; "EFKA-46,

EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450" available from Morishita Sangyo K.K. ; polymeric dispersants such as "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" available from San Nopco Limited; "Adeka Pluronics L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" available from ADEKA; and " IO ET (brand name) S-20" available from Sanyokasei Co. , Ltd. ; and the like.

[0053] These pigment dispersants may be used alone or as a combination of two or more of them. Especially, the pigment derivatives and polymeric dispersants are

preferably used in combination in the present invention. Further, the pigment dispersants of the present invention may be used as a combination of the terminally modified polymers, graft polymers or block polymers having an anchoring moiety for pigment surfaces with alkali-soluble resins. Such alkali-soluble resins include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, as well as acidic cellulose derivatives having a carboxylic acid in the side chain and resins obtained by modifying a

hydroxyl-containing polymer with an acid anhydride, among which (meth ) acrylic acid copolymers are especially preferred. The N-subst ituted maleimide monomer copolymers described in JP-A-H10 -300922 ; the ether dimer copolymers described in JP-A2004 - 300204 ; and the alkali-soluble resins containing a polymeri zable group described in JP-A-H7-319161 are also preferred.

[0054] In the case of aqueous dispersions, the dispersants described in paragraphs [0487] to [0516] of JP-A2012 - 158736 can be used.

[0055] The amount of the dispersants contained in the compositions of the present invention is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, even more preferably 10 to 60 parts by mass per 100 parts by mass of the pigment used as a colorant.

Specifically, the amount of the polymeric dispersants used is preferably in the range of 5 to 100 parts by mass, more preferably in the range of 10 to 80 parts by mass per 100 parts by mass of the pigment.

When the pigment derivatives are also used, the amount of the pigment derivatives used is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 3 to 20 parts by mass, especially preferably in the range of 5 to 15 parts by mass per 100 parts by mass of the pigment.

[0056] The content of the dispersants for preparing the pigment dispersions in the present invention is preferably 1 % by mass to 90 % by mass, more preferably 3 % by mass to 70 % by mass based on the total solids of the pigment in the pigment dispersions.

When a pigment is used as a colorant in combination with a pigment dispersant in a curable colored composition, the total content of the colorant and the dispersant is preferably 30 to 90 % by mass, more preferably 40 to 85 % by mass, even more preferably 50 to 80 % by mass based on the total solids of the curable colored composition to improve curing sensitivity and color density.

[0057] In the present invention, the pigments preferably have a volume average particle size of 10 nm or more and 250 nm or less. As used herein, the term "volume average particle size" of particles of a pigment refers to the particle size of the pigment itself, or the particle size of the pigment plus additives such as dispersants if such additives are deposited on the pigment. In the present invention, the volume average particle sizes of the pigments were measured by using Nanotrac UPA particle size analyzer (UPA-EX150 from Nikkiso Co. , Ltd. ) . The measurements were made according to a specific procedure using a measuring cell containing 3 ml of each pigment dispersion. As for input parameters during the measurements, ink viscosity was used as viscosity and the density of the pigment was used as the density of dispersed particles.

[0058] More preferably, the volume average particle size is 20 nm or more and 250 nm or less, still more preferably 30 nm or more and 230 nm or less. If the number average particle size of particles in a pigment dispersion is less than 20 nm, storage stability may not be ensured, but if it exceeds 250 nm, optical density may decrease.

[0059] Preferably, the concentration of the pigments in the pigment dispersions of the present invention is 0.1 to 50 % by weight, more preferably 3 to 45 % by weight, especially preferably 7 to 40 % by weight based on the total solids.

[0060] The pigments of the present invention are used by adjusting their properties such as solvent resistance, dispersibility and heat transfer with substituents to suit the purpose of their application. Further, the pigments of the present invention can be used in the

emulsified/dispersed state or solid dispersed state depending on the system used.

[0061] (Colored compositions)

The colored compositions of the present invention are characterized in that they comprise at least one of the pigments described above. Preferably, the colored compositions of the present invention are

radiation-sensitive colored compositions.

The colored compositions or radiation-sensitive colored compositions of the present invention can conveniently be used as color resist solutions, inks for inkjet printing, and colored compositions for color filters. The colored compositions of the present invention can be prepared by dispersing a pigment of the present invention in a vehicle. The colored compositions of the present invention include compositions without vehicle for inks. The colored compositions of the present invention may contain other additives as appropriate so far as the benefits of the present invention are not affected. The other additives include known additives ( de scr ibed in JP-A2003 - 306623 ) such as, e.g., anti-drying agents (wetting agents) , anti-fade agents, emulsion stabilizers, penetration promoters, UV absorbers, preservatives, anti-mold agents, pH modifiers, surf ace tension modifiers , defoamers, viscosity modifiers , dispersion stabilizers, anti-rust agents, chelating agents and the like. These various additives are directly added to ink solutions in the case of water-soluble inks. In the case of oil-soluble inks, they are typically added to pigment dispersions after the dispersions have been prepared, but they may be added to the oil phase or aqueous phase during preparation.

In addition, within the scope not deviating from the purpose of the present invention, the composition of the present invention may comprise other pigment and/or dye. The amount of such a pigment and/or dye is preferably 1% by weight or less, relative to all the colorant contained in the composition. For example, may be used the colorant disclosed in JP-A-S 64 - 90 03 , JP-A-S 6 - 91102 ,

JP-A-H01-94301, JP-A-HO 6-11614 , JP Registration No .

2592207, US Patent No. 4808501, US Patent No. 5667920, US Patent No. 505950, US Patent No. 5667920, JP-A-H 05 - 333207 , JP-A-H06-35183, JP-A-HO 6 - 51115 , JP-A-HO 6- 194828. As the structure thereof, dyes such as pyrazoleazo, anilinoazo, triphenylmethane, anthraquinone , benzylidene, oxonol, pyrazolo triazoleazo, pyridoneazo, cyanine, phenothiazine , pyrrolopyrazole azo. The dye may be a colorant multimeric complex. Such a colorant mult imeric complex may be exemplified by compounds disclosed in JP-A- 2011- 213925 or JP-A-2013-041097.

[0062] [Inkjet Ink]

The inkjet ink of the present invention (occasionally referred to as "ink", hereinafter) uses the pigment dispersion, and is preferably prepared by mixing water-soluble solvent, water and so forth. If there is no specific problem, the pigment dispersion of the present invention may be used as it is.

[0063] Content of the pigment dispersion in the ink of the present invention is preferably in the range from 1 to 100% by mass, taking hue of pictures formed on recording medium, color density, chroma and transparency into consideration, more preferably in the range from 3 to 20% by mass, and particularly in the range from 3 to 10% by mass.

[0064] Content of the pigment of the present invention, per 100 parts by mass of the ink of the present invention, is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less, and furthermore preferably 1 to 10 parts by mass. In the ink of the present invention, other pigment may be used together with the pigment of the present invention. When two or more species of the pigments are used in combination, the total content of the pigments preferably falls in the above-described ranges.

[0065] The ink of the present invention may be used not only for formation of monochromatic image, but also for formation of full-color image. Magenta ink, cyan ink and yellow ink may be used for forming full-color image, and black ink may be used additionally for color adjustment.

[0066] In the ink of the present invention, other pigment may be used together with the above-described pigment. Examples of yellow pigment usable therefor include

C.I.P.Y.74, C.I.P.Y.128, C.I.P.Y.155 and C.I.P.Y.213, examples of magenta pigment usable therefor include C.I.P.V.19 and C.I.P.R.122, and examples of cyan pigment usable therefor include C. I. P. B.15:3 and C . I . P . B .15 : . Besides them, arbitrary pigment may be used for each color. Examples of black color material usable therefor include disazo, trisazo and tetrazo pigments, and carbon black dispersion.

[0067] The water-soluble solvent usable for the inkjet ink of the present invention include polyhydric alcohols, polyhydric alcohols derivative, nitrogen-containing solvent, alcohols, and sulfur-containing solvent.

Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1 , 5-pentanediol , 1 , 2 , 6-hexanet riol , and glycerin.

[0068] Examples of the polyhydric alcohol derivative include ethylene glycol monomethyl ether, ethylene glycol monoethylether , ethylene glycol monobutyl ether,

diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and ethylene oxide adduct of diglycerin.

[0069] Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2 -pyrrol idone , cyclohexyl

pyrrolidone, and t r iet hanolamine , examples of alcohol include ethanol, isopropanol, butanol and benzyl alcohol, and examples of the sulfur-containing solvent include thiodiethanol , thiodiglycerol , sulfolane and

dimethylsulfoxide . Besides them, also propylene carbonate, ethylene carbonate and so forth may be used.

[0070] The water-soluble solvent used in the present invention may be used independently, or two or more species of which may be mixed. Content of the water-soluble solvent is 1% by mass or more and 60% by mass or less of the total ink, and preferably 5% by mass or more and 40% by mass or less. If the content of the water-soluble solvent in the ink is less than 1% by mass, a sufficient level of optical density will not be obtained in some cases, whereas if the content exceeds 60% by mass, the ink liquid may be more viscous, and may be destabilized in the injection

performance .

[0071] Preferable characteristics of the inkjet ink of the present invention are as follow.

Surface tension of the ink is preferably 20 mN/m or larger and 60 mN/m or smaller, more preferably 20 mN/m or larger and 45 mN/m or smaller, and further preferably 25 mN/m or larger and 35 mN/m or smaller. If the surface tension is smaller than 20 mN/m, the liquid may spill out over the surface of a nozzle of a recording head, and may inhibit normal printing. On the other hand, if the surface tension exceeds 60 mN/m, the ink may be less permeable into a recording medium after printing, and may increase the drying time.

The surface tension was measured similarly as described above, using a ilhelmy surface tensiometer, under an environment of 23°C, 55%RH.

[0072] Viscosity of the ink is preferably 1.2 mPa-s or larger and 8.0 mPa-s or smaller, more preferably 1.5 mPa- s or larger and smaller than 6.0 mPa-s, and further preferably 1.8 mPa-s or larger and smaller than 4.5 mPa- s. If the viscosity exceeds 8.0 mPa ^■ s , the ink may be degraded in the ejection performance. On the other hand, if the viscosity is smaller than 1.2 mPa-s, the ink may be degraded in the long-term injection performance.

The viscosity (including those described later) was measured using a rotational viscometer, Rheomat 115 (from Contraves Advanced Devices Sdn. Bhd.), at 23°C and at a shearing speed of 1400 s ^"1 .

[0073] Besides the above-described components, the ink will be added with water, within the range capable of adjusting the surface tension and viscosity in the preferable ranges described above. Amount addition of water, although not specifically limited, is preferably 10% by mass or more and 99% by mass or less of the total mass of ink, and more preferably 30% by mass or more and 80% by mass or less .

[0074] For further needs of characteristic control such as improving the ejection performance, the ink may be used together with polyethylene imine, polyamines,

polyvinylpyrrolidone, polyethylene glycol, cellulose derivatives such as ethyl cellulose and carboxymethyl cellulose, polysaccharides and derivatives thereof, water-soluble polymer, polymer emulsions such as acrylic polymer emulsion, polyurethane-based emulsion and

hydrophilic latex, hydrophilic polymer gel, cyclodextrin , large cyclic amines, dendrimer, crown ethers, urea and derivatives thereof , acetamide, silicone-based surfactant , and fluorine-containing surfactant.

[0075] In addition, for the purpose of adjusting

electro-conductivity and pH, possibly used are alkali metal compounds such as potassium hydroxide, sodium hydroxide and lithium hydroxide, nitrogen-containing compounds such as ammonium hydroxide, triethanolamine , diethanolamine , ethanolamine and 2 -amino-2 -methy1 - 1 -propano 1 , alkali earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, and salts formed between strong acid and weak alkali such as ammonium sulfate.

Examples of other additives to be added optionally include pH buffering agent , antioxidant, ant i-mold agent , viscosity modifier, conducting agent, and UV absorber.

[0076] [Color resist solutions]

The curable colored compositions of the present invention are characterized in that they comprise at least one of the pigments described above. Preferably, the curable colored compositions are radiation-sensitive colored compositions that are cured by radiations.

Preferably, the radiation-sensitive colored compositions of the present invention further contain an alkali-soluble resin, a polymerizable compound, a polymerization initiator and a solvent .

During the preparation of the radiation-sensitive colored compositions of the present invention, the pigments obtained as described above may be directly added or the pigments dispersed in solvents may be added. The pigments are preferably added as pigment dispersions because excellent color properties, durability, dispersion stability, light resistance and weatherability are achieved .

[0077 ] Amount of use of the pigment (if any other pigment (s) are used in combination, the total amount of the pigment (s) ) in the radiation-sensitive composition of the present invention is preferably 0.01 to 2 parts by mass per 1 part by mass of the polymeri zable compound, and more preferably

0.1 to 1 part by mass.

[0078] <Alkali-Soluble Resin>

The colored radiation-sensitive composition of the present invention more preferably contains an alkali-soluble resin. By containing the alkali-soluble resin, the composition may be improved in the developability and pattern formability.

[0079] The alkali-soluble resin is arbitrarily selectable from those in the form of straight organic high-molecular polymer, and having, in the molecule thereof (more preferably, in the molecule having an acrylic copolymer or a s tyrene-based copolymer as the principal chain) , at least one group capable of enhancing alkali solubilization.

[0080] In the process of preparing the alkali-soluble resin by the radical polymerization, any of publicly-known methods based on radical polymerization may be used.

Conditions of polymerization in the process of preparing the alkali-soluble resin by radical polymerization, such as temperature, pressure, species and content of radical initiator, species of solvent and so forth, are readily set by those skilled in the art, and may also be determined experimentally .

[0081] The straight organic high-molecular polymer used as the alkali-soluble resin is preferably polymers having carboxylic acid in the side chain thereof, examples of which include methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterif ied maleic acid copolymer, alkali-soluble phenol resins such as novolac resin, and acidic cellulose derivatives having carboxylic acids in the side chains thereof, and adducts of polymer having hydroxy groups with acid anhydrides. In particular, copolymers of (meth ) acrylic acid and other monomers co-polymeri zable therewith are preferable as the alkali-soluble resin. The other monomers co-polymeri zable wit h the (meth) acrylic acid are exemplified by alkyl (meth ) acrylate , aryl

(meth ) acrylat e , and vinyl compounds. Examples of the alkyl (meth ) acrylate and aryl (meth) acrylate include methyl (meth ) acrylate , ethyl (meth) acrylate, propyl (meth ) acrylate , butyl (meth ) acrylate , isobutyl

(meth ) acrylate , pentyl (meth) acrylate, hexyl

(meth ) acrylate , octyl (meth ) acrylate , phenyl

(meth ) acrylate , benzyl (meth) acrylate,

tolyl (meth) acrylate, naphthyl (meth ) aerylat e , cyclohexyl (meth ) acrylate , and the vinyl compounds are exemplified by styrene, -methy1 styrene , vinyltoluene , glycidyl

methacrylate, acrylonitrile , vinyl acetate,

N-vinylpyrrolidone , tetrahydrofurfuryl methacrylate, polystyrene macromonomer , polymethyl methacrylate macromonomer , and N-substituted maleimide monomers described in JP-A-H10-300922 such as N-phenylmaleimide and N-cyclohexyl maleimide. These other monomers

co-polymeri zable with (meth ) acrylic acid may be used alone by itself, or two or more species of which may be combined.

[0082] As the alkali-soluble resin, also preferably used is a polymer (a) configured by polymerizing a monomer component which essentially contains the compound represented by the formula (ED) below (also referred to as "ether dimer", hereinafter).

Formula (ED) (In the formula (ED), each of R ¹ and R ² independently represents a Ci_ ₂ 5 hydrocarbon group which may have a hydrogen atom or subst ituent . ) The alkali-soluble resin also preferably contains the polymer (a), configured by polymerizing a monomer component which essentially contains the compound represented by the formula (ED), as an essential polymer component (A). By the configuration, the curable resin composition of the present invention can form a cured coated film quite excellent in heat resistance and transparency. In the formula (ED) which represents the ether dimer, the Ci_25 hydrocarbon group represented by R ¹ and R ² , and which may have a substituent, is not specifically limited, wherein examples of which include straight chain-like or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl groups; aryl group such as phenyl group; alicyclic groups such as cyclohexyl, t-butyl cyclohexyl, dicyclopentadienyl , tricyclodecany1 , isobornyl, adamantyl, and 2-methyl-2-adamantyl groups; alkyl groups substituted by alkoxy such as 1-methoxyethyl , and 1-ethoxyethyl groups; and alkyl group substituted by aryl group such as benzyl group. Among these, substituents having a primary or secondary carbon such as methyl, ethyl, cyclohexyl, and benzyl groups, which are less eliminatable by acid or heat, are particularly preferably from the viewpoint of heat resistance.

[0083] Specific examples of the ether dimer usable in the present invention are referred to those described in paragraphs [0242] to [0244 ] of JP-A-2012 - 063735.

[0084] As the alkali-soluble phenol resin, the the colored curable composition of the present invention is preferably used when it is configured as a positive composition. The alkali-soluble phenol resin is exemplified by novolac resins and vinyl polymers.

The novolac resins are exemplified by those obtained by allowing phenols and aldehydes to condense under the presence of an acid catalyst. The phenols are exmplified by phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol , catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.

The aldehydes are exemplified by formaldehyde,

paraformaldehyde, acetoaldehyde , propionaldehyde , and benzaldehyde .

The phenols and the aldehydes may be used independently, or two or more species of which may be combined.

[0085] Specific examples of the novolac resins include condensate of metacresol, paracresol or mixture thereof with formalin.

[0086] The novolac resin may be adjusted in the molecular weight distribution typically by means of fractionation. The novolac resin may also be mixed with a low molecular weight component having a phenolic hydroxy group, such as bisphenol C or bisphenol A.

The alkali-soluble phenol resin may comprise a structural unit derived from an ethylenic unsaturated monomer represented by the formula (X).

wherein R ¹ represents hydrogen atom or methyl group, R ² represents an alkylene group having 2 to 10 of carbon atoms, R ³ represents hydrogen atom or an alkyl group having 1 to 20 of carbon atoms which may comprise a benzene ring, n is an integer of 1 to 15.

In the above formula (X) , the carbon number of alkylene group as R ² is preferably 2 to 3. The carbon number of alkyl group as R ³ is 1 to 20, preferably 1 to 10, and the alkyl as R ³ may comprise a benzene ring. The alkyl group comprising a benzene ring represented by R ³ is exemplified by benzyl group and 2 -phenyl ( i so ) propyl group.

[0087] In order to improve crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymeri zable group may be used. Examples of the useful alkali-soluble resin having a polymerizable group include those having, in the side chain thereof, allyl group, (meth)acryl group, al l.yloxyal ky1 group and so forth. Examples of the polymer having a polymerizable group include Dianal NR Series (from

Mitsubishi Rayon Co. Ltd.), Photomer 6173 (COO-H-containing polyurethane acrylic oligomer, from Diamond Shamrock Co. Ltd. ) , Viscoat R-264, KS Resist 106 (both from Osaka Organic Chemical Industry Ltd.), Cyclomer P Series, Placcel CF200 Series (both from Daicel Chemical Industries, Ltd.), and Ebecryl 3800 (from Daicel-UCB Co. Ltd.) . Preferable examples of such alkali-soluble resins having a

polymerizable group include urethane-modified

polymer i zable double bond-containing acrylic resin obtained by preliminarily allowing isocyanate groups to react with OH groups, while leaving one isocyanate group unreacted, and by allowing a (meth ) acryloyl

group-containing compound to react with a carboxy group-containing acrylic resin; unsaturated

group-containing acrylic resin obtained by allowing a carboxy group-containing acrylic resin to react with a compound having in the molecule thereof both of an epoxy group and a polymerizable double bond; acid-pendant epoxy acrylate resin; polymerizable double bond-containing acrylic resin obtained by allowing an OH group-containing acrylic resin to react with a dibasic acid anhydride having a polymerizable double bond; resin obtained by allowing an OH group-containing acrylic resin, isocyanate, and a polymerizable group-containing compound to react together; and a resin obtained by subjecting a resin having in the side chain thereof an ester group which has an leaving group such as halogen atom or sulfonate group at the a- or β-position, as described in JP-A-2002 -229207 and

JP-A-2003-335814 , to a base treatment.

[0088] Particularly preferable examples of the

alkali-soluble resin include benzyl

(meth) acrylate/ (meth) acrylic acid copolymer, and

multi-component copolymer composed of benzyl

(meth) acrylate/ (meth) acrylic acid/other monomer. Other examples include copolymer containing 2 -hydroxyethy1 methacrylat e , and 2 -hydroxypropyl

(meth) acrylate/polystyrene macromonomer /benzyl

methacrylate/methacrylic acid copolymer,

2-hydroxy-3-phenoxypropyl aerylat e/polymethyl

methacrylate macromonomer /benzyl

methacrylate/methacrylic acid copolymer, 2 -hydroxyethy1 methacrylate /polystyrene macromonomer /methyl

methacrylate/methacrylic acid copolymer, 2 -hydroxyethy1 methacrylate/polystyrene macromonomer /benzyl methacrylate/methacrylic acid copolymer described in JP-A-H07-140654.

[0089] Acid value of the alkali-soluble resin is preferably 30 mg KOH/g to 200 rag KOH/g, more preferably 50 mg KOH/g to 150 mg KOH/g, and most preferably 70 to 120 mg KOH/g. Weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

As far as particularly not described, the weight average molecular weight is that measured by Gel permeation chromatography (GPC) . GPC is measured by removing the solvent from an obtained polymer to isolate the solid, diluting the obtained solid by tetrahydrofuran to be a concentration of 0.1% by mass, and then using HLC-8020GPC manufactured by Tosoh Corporation and a column which is formed by serially joining three columns being TSKgel Super Multipore HZ-H manufactured by Tosoh Corporation and having 4.6mm ID and 15 cm length. The condition was that the sample concentration was 0.35% by weight, flow velocity was 0.35 mL/min, the injection amount was 10 μ!>, and the measuring temperature was 40°C, and RI detector is used.

[0090]

Content of the alkali-soluble resin in the colored curable composition is preferably 1 to 15% by mass of the total solid content of the composition, more preferably 2 to 12% by mass, and particularly 3 to 10% by mass.

[0091] <Polymeri zable Compound>

The polymeri zable compound is arbitrarily selectable taking manufacturing process of the color filter into

consideration. The polymeri zable compound is exemplified by photo-sensitive compound and/or thermosetting compound, wherein the photo-sensitive compound is particularly preferable .

The polymeri zable compound is selected, more specifically, from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds. This sort of compound has widely been known in the related industrial field, and may be used also in the present invention without specific limitation. The compound may have any chemical form including monomer, prepolymer, that is, dimer, trimer and oligomer, or mixture of them, and multimer of them. The polymeri zable compound in the present invention may be used alone by itself, or two or more species of which may be combined .

[0092] More specifically, examples of the monomer and the related prepolymer include unsaturated carboxylic acid (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters and amides thereof, and multimers thereof. Among these, preferable are esters formed between unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, amides formed between unsaturated carboxylic acid and aliphatic polyvalent amine compound, and multimers thereof. Other preferable examples include addition product formed between the unsaturated carboxylic esters or amides having a nucleophilic substituent such as hydroxy group, amino group or mercapto group, and a monofunct ional or polyfunct ional isocyanate or epoxy compound; and dehydration condensation product formed between the unsaturated carboxylic esters or amides, and a monofunctional or polyfunct ional

carboxylic acid. Furthermore preferable examples include addition product formed between unsaturated carboxylic esters or amides having an electrophilic substituent such as isocyanate group or epoxy group, and a monofunct ional or polyfunct ional alcohols, amines or thiols, and

substitution product formed between unsaturated carboxylic esters or amides having a leaving substituent such as halogen-containing group or tosyloxy group, and

monofunct ional or polyfunct ional alcohols, amines or thiols. Besides them, also usable are compounds having unsaturated phosphoni-c acid, vinylbenzene derivative such as styrene, vinylether, and ally! ether, in place of the above-described unsaturated carboxylic acid.

As specific examples of these compounds, the compounds described in paragraphs [0095] to [0108] of

JP-A-2009-288705 are preferably used also in the present invention .

[0093] The polymeri zable compound is also preferably a compound having an ethylenic unsaturated group and having a boiling point under normal pressure of 100°C or higher, which is composed of polymeri zable monomers each having at least one addit ion-polymeri zable ethylene group. Specific examples include monofunct ional acrylate or methacrylate such as polyethylene glycol mono (meth ) acrylate ,

polypropylene glycol mono (meth ) aerylate , and phenoxyethyl (meth ) acrylate ; polyfunct ional acrylate or methacrylate such as polyethylene glycol di (meth ) acrylate , trimethylol ethane tri (meth ) acrylate , neopentyl glycol

di (meth) acrylate, pentaerythritol tri (meth ) acrylate , pentaerythritol tetra (meth ) acrylate , dipentaerythritol penta (meth ) aerylate , dipentaerythritol

hexa (meth ) acrylate , hexanediol (meth ) aerylate ,

trimethylolpropane tri ( acryloyloxypropyl ) ether, and tri ( acryloyloxyethyl ) isocyanurate ; addition product of polyhydric alcohol such as glycerin or trimethylol ethane with ethylene oxide or propylene oxide, followed by esterification with (meth) acrylate; urethane

(meth) acrylates described in JP-B- S 48 - 41708 , JP-B-S50-6034 and JP-A-S 51 - 37193 ; polyester acrylates described in JP-A-S48-64183, JP-B- S49- 43191 and JP-B-S 52 - 30490 ;

polyfunct ional acrylate or methacrylate such as epoxy acrylate, obtained as a reaction product between epoxy resin and (meth ) acryl ic acid; and mixtures of them.

Commercially available products of these polymeri zable compound include urethane oligomers UAS-10, UAB-140 (from Sanyo Kokusaku Pulp Co. Ltd.), UA-7200 (from Shin-Nakamura Chemical Co . Ltd . ) , DPHA-4 OH (from ippon Kayaku Co . Ltd . ) , UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (from Kyoeisha Chemical Co. Ltd.), and M-460 (from Toagosei Co. Ltd. ) .

Also exemplified is a polyfunct ional (meth ) acrylate obtained by allowing polyfunct ional carboxylic acid to react with a compound, such as glycidyl (meth ) acrylat e , having a cyclic ether group and an ethylenic unsaturated grou .

Other preferable examples of the polymeri zable compound include compounds having a fluorene ring, and two or more ethylenic polymeri zable groups, such as those described in JP-A-2010-160418, JP-A-2010 - 129825 , Japanese Patent 4364216, and cardo resin.

[0094] Preferable examples of the compound having a boiling point under normal pressure of 100°C or higher, and having at least one addit ion-polymeri zable ethylenic unsaturated group include the compounds described in paragraphs [0254] to [0257] of JP-A-2008-292970.

[0095] Besides them, also radical polymeri zable monomers described in paragraphs [0191] to [0193] of

JP-A-2011-180307 , and those represented by formulae ( O-1) to (MO-5) in paragraphs [0093] to [0094] of JP-A-2012 - 046712 are preferably used.

[0096] Compounds represented by the formulae (1) and (2) in JP-A-H10-62986, with specific examples shown therein, which are obtainable by adding ethylene oxide or propylene oxide to polyhydric alcohol, followed by estrification with

(meth ) aerylate , are usable as the polymeri zable compound.

[0097] Among others, preferable examples of the

polymeri zable compound include dipentaerythri tol

triacrylate (commercially available as KAYARAD D-330, from Nippon Kayaku Co. Ltd.), dipentaerythritol tetraacrylate

(commercially available as KAYARAD D-320, from Nippon Kayaku Co. Ltd.), dipentaerythritol penta (meth ) aerylate

(commercially available as KAYARAD D-310, from Nippon Kayaku Co. Ltd.), dipentaerythritol hexa (meth ) acrylate (commercially available as KAYARAD DPHA, from Nippon Kayaku Co. Ltd.), and those having structures in which these

(meth ) aeryloyl group are bonded through an ethylene glycol or propylene glycol residues. Also oligomer of these polymeri zable compounds may be used.

[0098] The polymeri zable compound may also be a

polyfunct ional monomer, having an acid group such as carboxy group, sulfonate group, phosphate group or the like.

Accordingly, the ethylenic compound may be used as it is, if the compound is used in the form of mixture as described in the above, with its unsaturated carboxy group kept therein. Alternatively, if necessary, the ethylenic compound may be introduced with an acid group, by allowing the hydroxy group thereof to react with a non-aromatic carboxylic anhydride. Specific examples of the non-aromatic carboxylic anhydride usable herein include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride , succinic anhydride, and maleic anhydride.

[0099] In the present invention, the monomer having an acid group is an ester formed between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which is preferably a polyfunct ional monomer introduced with an acid group obtained by allowing an unreacted hydroxy groups of an aliphatic polyhydroxy compound to react with a

non-aromatic carboxylic anhydride, and particularly an ester in which the aliphatic polyhydroxy compound is pentaerythri t ol and/or dipent aerythri tol . Examples of commercially available product include M-510 and M-520, which are polybasic acid-modified acrylic oligomer from Toagosei Co. Ltd.

[0100] While each of these monomers is used alone by itself, two or more species of which may be used in a mixed manner, since it is difficult to use a single compound in the process of manufacturing. It is also possible to use as the monomers , if necessary, an acid group-free polyfunct ional monomer and an acid group-containing polyf unct ional monomer in

combination.

Acid value of the acid group-containing polyfunct ional monomer is preferably 0.1 to 40 mg KOH/g, and particularly 5 to 30 mg KOH/g. A too small acid value of the

polyfunct ional monomer may degrade the solubility

characteristic in the process of development, whereas a too large acid value may degrade readiness in manufacturing and handling, may degrade phot o-polymeri zation ability , and may degrade curing performance enough to ensure surface smoothness over pixels. Accordingly, when two or more species of the polyfunct ional monomers having different acid groups are used, or when the acid group-free

polyfunct ional monomer is used in combination, it is essential to adjust the acid value of the whole

polyfunct ional monomer in the above-described ranges.

The polymeri zable compound preferably contains

polyfunct ional monomer having a caprolactone structure as the polymeri zable monomer, wherein the polyfunctional monomer having a caprolactone structure usable herein includes those described in paragraphs [0155] to [0162] in JP-A-2012-003225.

[0101] The polymeri zable compound also preferably contains, as the polymerizable monomer, a monomer selected from the compound group represented by the formula (i) or (ii) described in paragraphs [0029] to [0040] of

JP-A-2010-085457.

[0102] Also acid group-containing ethylenic unsaturated compounds are suitable for the polymerizable compound. The acid group-containing ethylenic unsaturated compounds are obtained typically by converting a part of hydroxy groups of a polyhydric alcohol into (meth ) acrylate , and by adding an acid anhydride to the residual hydroxy groups so as to convert them to carboxy groups. Commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomer from Toagosei Co. Ltd.

Also polyhydric thiol compound having two or more mercapto (SH) groups in one molecule is suitable as the polyhydric thiol compound. The polyhydric thiol compound usable herein include those described in paragraphs [0038] to [0040] of JP-A-2009-086563.

The polymerizable compounds also preferably include alkyleneoxy-containing polymerizable compounds.

Alkyleneoxy-containing polymerizable compounds that can be used include the polymerizable compounds described in paragraphs [0031] to [0047 ] of JP-A2009 - 17572 .

[0103] Content of the polymerizable compound is 20 to 90% by mass, and preferably 40 to 80% by mass. [0104] Content of the polymerizable compound is preferably 40 to 95% by mass of the total solid content of the color filter, and more preferably 50 to 90% by mass. The composition may be added with other resins if necessary, wherein the total content including those of other resins preferably falls within the above-described ranges. Note that the total solid content means the amount of components which remain in the form of solid after the composition is dried and cured, containing no solvent, but containing monomers.

[0105] <Polymerization Initiator>

The colored radiation-sensitive composition of the present invention preferably contains a polymerization initiator. The polymerization initiator is not specifically limited so long as it can initiate polymerization of the

polymerizable compound, and is selectable arbitrarily from publicly known photo-polymerization initiators.

Preferable examples include those having photo-sensitivity in the region from ultraviolet radiation to visible light, such as an activator which interacts in some way with a photo-excited sensitizer to thereby produce an activated radical, and an initiator which initiates cationic polymerization depending on types of monomer.

The photo-polymerization initiator preferably contains at least one component having a molecular absorption

coefficient of approximately 50, in the wavelength range from approximately 300 to 800 nm (more preferably from 330 to 500 nm) .

[0106] Examples of the photo-polymerization initiator include halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compound such as acylphosphine oxide, oxime compounds such as hexaaryl biimidazole and oxime derivatives, organic peroxide, thio compound, ketone compound, aromatic onium salt, ketoxime ether,

aminoacetophenone compound, and hydroxyacet ophenone .

[0107] Examples of the halogenated hydrocarbon compound having a triazine skeleton include the compounds described in Wakabayashi et al . , Bull. Chem. Soc. Japan, 42, 2924(1969), the compounds described in British Patent No. 1388492, the compounds described in JP-A-S53-133428 , the compound described in German Patent No. 3337024, the compounds described in F. C. Schaefer et al., J. Org. Chem., 29, 1527(1964), the compounds described in JP-A-S62-582 1 , the compounds described in JP-A-H05-281728 , the compounds described in JP-A-HO 5- 34920 , and the compounds described in United States Patent No. 4212976.

[0108] Examples of the photo-polymerization initiator usable herein, other than those described above, include the polymerization initiators described in paragraph [0116] in JP-A-2012-053243.

[0109] The ketone compound usable herein include those described in paragraph [0117] of JP-A-2012-053243.

[0110] Also hydroxyacet ophenone compound,

aminoacetophenone compound, and acylphosphine compound are preferably used as the photo-polymerization initiator. More specifically, also the aminoacetophenone-based initiators described in JP-A-H10 -291969 , and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 may be used.

Examples of the hydroxyacet ophenone-based initiator usable herein include I rgacure- 184 , Darocur- 1173 , Irgacure-500 , Irgacure-2959 and Irgacure-127 (trade names, all from BASF GmbH) . Examples of the aminoacetophenone-based initiator usable herein include commercially available I rgagure- 907 , Irgacure-369 and Irgacure-379 (trade names, all from BASF GmbH) . Also the compounds described in JP-A-2009- 191179 , the absorption wavelength of which being matched to long wavelength sources of 365 nm or 405 nm, are used as the aminoacetophenone-based initiator. Examples of the acylphosphine-based initiator usable herein include commercially available Irgagure-819 and Darocur-TPO (trade names, both from BASF GmbH) .

[0111] The photo-polymerization initiator is more

preferably exemplified by oxime-based compound. Specific examples of the oxime-based initiator include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068 , and the compounds described in

JP-A-2006-342166.

[0112] Examples of the oxime compound such as oxime derivatives, preferably used in the present invention as the photo-polymerization initiator, include

3-benzoyloxyiminobutane-2-one,

3 -acetoxyiminobutane- 2 -one ,

3-propionyloxyiminobutane-2-one,

2-acetoxyiminopentane-3-one ,

2-acetoxyimino-l-phenylpropane-l-one,

2-be zoyloxyimino- 1 -phenylpropane-1 -one ,

3- ( 4 -1oluenesul fonyloxy ) iminobutane-2-one , and

2-ethoxycarbonyloxyimino-l-phenylpropane-l-one.

[0113] Examples of the oxime ester compound include the compounds described in J. C. S. Perkin II (1979), pp.1653-1660; J. C. S. Perkin II (1979), pp.156-162; Journal of Photopolymer Science and Technology (1995) , pp.202-232; JP-A-2000-66385, JP-A-2000-80068, Published Japanese Translation of PCT International Publication for Patent Application (JP, A) No. 2004-534797, and JP-A-2006-342166. Commercially available products preferably used herein include Irgagure-OXEOl and Irgagure-OXE02 (both from BASF GmbH) . In addition, commercial products such as TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-305 which are manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) may be used.

[0114] Examples of the oxime ester compound usable herein, other than those described above, include the compounds having oximes linked to the nitrogen atom of carbazole ring as described in Published Japanese Translation of PCT International Publication for Patent Application (JP, A) No. 2009-519904; the compounds having a hetero-subst ituent at the benzophenone portion as described in United States Patent No. 7626957; the compounds having a nitro group introduced in the dye moiety as described in JP-A-2010 - 15025 and United States Patent No. 2009/292039; the

ketoxime-based compounds described in International Patent No. 2009-131189; the compounds having a triazine skeleton and an oxime skeleton in one molecule as described in United States Patent No. 7556910; and the compounds showing an absorption maximum at 436 nm and is therefore highly sensitive to g-line source as described in

JP-A-2009-221114.

[0115] Also the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007 - 32274 are suitably used. Among the cyclic oxime compounds, those bound to a carbazole dye to form a condensed ring therewith, described in

JP-A-2010-32985 and JP-A-2010 - 185072 , are particularly preferable in view of sensitizing, by virtue of their large light absorbance.

Also the compounds having an unsaturated bond at a specific site of the oxime compound, described in JP-A-2009-242469 , are suitably used, since they can regenerate an activated radical from a polymerization-inactive radical.

[0116] Particularly preferable examples include the oxime compounds having a specific substituent as described in JP-A-2007-269779, and the oxime compounds having a thioaryl group as described in JP-A-2009-191061.

More specifically, the oxime-based photo-polymerization initiator described in JP-A-2012-032556 is preferably used.

[0117] Two or more species of the radical

photo-polymerization initiator, usable in the present invention, may be used in combination depending on needs. Content of the radical photo-polymerization initiator in the radiation-sensitive composition (the total content, if two or more species are contained) is preferably in the range from 0.1 to 20% by mass of the total solid content of the radiation-sensitive composition, more preferably in the range from 0.5 to 10% by mass, and particularly in the range from 1 to 8% by mass. In these ranges, good levels of sensitivity and pattern formability may be obtained.

[0118] In the present invention, a sensitizer may be contained for the purpose of improving radical generation efficiency, and of shifting the photosensitive wavelength towards the longer side. The sensitizer usable in the present invention is preferably any of those capable of sensitizing the radical photo-polymerization initiator by an electron transfer mechanism or energy transfer

mechanism .

[0119] The sensitizer usable in the present invention is exemplified by the compounds described in paragraphs [0101] to [0154] of JP-A-2008-32803.

Content of the sensitizer is preferably 0.1% by mass to 20% by mass on the basis of solid content, and more preferably 0.5% by mass to 15% by mass, from the viewpoint of photo-absorption efficiency in the deep portion and degradation efficiency for initiation.

The sensitizer may be used independently, or two or more species of which may be combined.

[0120] <Other Components>

[Organic Solvent]

The colored radiation-sensitive composition of the present invention may contain at least one species of organic solvent .

The organic solvent is not specifically limited so long as it satisfies solubility of co-existing components, and coatability of the resultant colored curable composition, and is preferably selected in particular taking solubility of binder, coatability and safety into account.

[0121] Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl

propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl

oxyacetate (specifically, methyl me t hoxyace t at e , ethyl methoxyacet at e , but yl methoxyacet at e , methyl ethoxyacet at e , ethyl ethoxyacet at e ) ) , alkyl 3 -oxypropi ona t es (e.g. , methyl 3-oxypropionate , and 3-oxypropionate ethyl

(specifically, methyl 3-methoxypropionate, ethyl

3-methoxypropionat e , methyl 3-ethoxypropionate , and ethyl 3-ethoxypropionate) ) , alkyl 2-oxypropionates (e.g., methyl 2 -oxypropionate , ethyl 2 -oxypropionate , and propyl 2-oxypropionate (specifically, methyl 2 -methoxypropionate , ethyl 2-methoxypropionate , propyl 2 -methoxypropionate , methyl 2 -ethoxypropionat e , and ethyl 2 -ethoxypropionate ) ) , methyl 2 -oxy-2 -methyl propionate, ethyl 2-oxy-2-methyl propionate (specifically, methyl 2-methoxy-2-methyl propionate, ethyl 2-ethoxy-2-methyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl

acetoacetate , ethyl acet oacetate , methyl 2-oxobutanate , and ethyl 2-oxobutanate.

[0122] Ethers are exemplified by those described, for example, in JP-A-2012 - 046712. Ketones are exemplified by methylethylketone , cyclohexanone , 2-heptanone, and

3-heptanone. Aromatic hydrocarbons are preferably

exemplified by toluene and xylene.

[0123] Two or more species of these organic solvents may be mixed, from the viewpoints of the above-mentioned solubility of the individual components, solubility of an alkali-soluble polymer if it is contained, and improvement in coated surface, possibly referring to the combinations described in JP-A-2012 - 0 6712.

[0124] Content of the organic solvent in the coloring composition is preferably determined so as to adjust the total solid content of the composition to 10% by mass to 80% by mass, and more preferably to 15% by mass to 60% by ma s s .

[0125] [Crosslinking Agent]

The colored curable composition for the color filter of the present invention may be added supplementally with a crosslinking agent so as to increase hardness of the colored cured film obtained by curing the colored curable

composition.

The crosslinking agent is not specifically limited so long as it can cure the film by a crosslinking reaction, and is exemplified by (a) epoxy resin, (b) melamine compound, guanamine compound, glycoluril compound or urea compound, ^■ substituted by at least one substituent selected from methylol group, alkoxymethyl group and acyloxymethy1 group, and (c) phenol compound, naphthol compound or hydroxyanthracene compound, substituted by at least one substituent selected from methylol group, al koxymethyl group, and acyloxymethy1 group. Among these,

polyfunct ional epoxy resin is preferable.

Specific examples and other details of the crosslinking agent are referred to the description in paragraphs [0134] to [0147] of JP-A-2004-295116.

[0126] The coloring composition of the present invention may contain the surfactant.

Copolymer used as the surfactant preferably has a weight average molecular weight (Mw) of 1,500 or larger and 5,000 or smaller.

The surfactant may be used independently, or two or more species of which may be combined.

Content of the surfactant in the pigment coloring composition of the present invention is preferably 10 parts by weight or less per 100 parts by weight of specific resin, more preferably 0.01 to 10 parts by weight, and furthermore preferably 0.01 to 1 part by weight.

[0127] The coloring composition of the present invention may contain the dispersant. Content of the dispersant is preferably 60 parts by weight or less per 100 parts by weight of specific resin, more preferably 5 to 45 parts by weight, and furthermore preferably 10 to 40 parts by weight.

[0128] [Polymerization inhibitors]

The curable colored compositions of the present invention should desirably contain a small amount of a polymerization inhibitor to inhibit undesired thermal polymerization of the polymerizable compounds during the preparation or storage of the curable colored compositions.

Polymerization inhibitors that can be used in the present invention include hydroquinone , p-methoxyphenol ,

di-t-butyl-p-cresol , pyrogallol, t-butylcatechol , benzoquinone, 4, 4' -thiobis (3-methyl-6-t-butylphenol) , 2,2' -methylenebis ( 4-methyl-6-t-butylphenol ) ,

N-nitrosophenylhydroxylamine cerous salt and the like. The amount of the polymerization inhibitors to be added is preferably about 0.01 % by mass to about 5 % by mass based on the total mass of the compositions.

[0129] <Preparation of Colored Radiation-Sensitive

Composit ion>

Modes of preparation of the colored radiation-sensitive composition of the present invention are not specifically limited, and may be such as mixing pigment, polymer i zable compound, and optionally-added photo-polymerization initiator and various additives, and further mixing the residual solvent.

[0130] In the process of preparing the colored curable composition for color filter of the present invention, the mixture of the various components is preferably filtered through a filter, in order to remove foreign matters and to reduce defects. The filter used herein is arbitrarily selectable from those having been used for filtration in general, without special limitation. Specific examples include those composed of fluorine-containing resin such as PTFE (polytetraf luoroe t hy lene ) ; polyamide-based resin such as nylon-6 and nylon-6,6; and polyolefin resin such as polyethylene and polypropylene (PP) (including those of high-density type, and ultra-high molecular type) . Among these filter materials, the polyamide-based resin such as nylon-6 and nylon-6,6, and polypropylene (including high-density polypropylene) are preferable.

Pore size of the filter is suitably 0.01 to 7.0 μιη or around, preferably 0.01 to 2.5 μιη or around, and more preferably 0.01 to 2.0 ]im or around. In these ranges, fine foreign matters, which possibly inhibit preparation of uniform colored curable composition in the later process, may extensively be removed, so as to ensure formation of a uniform and smooth colored curable composition.

[0131] The filter used herein may be a combination of different kinds of filters. In this case, filtering through a first filter may be conducted once, or twice or more. Alternatively, a plurality of filters with different pore sizes, within the above-described ranges, may be combined to configure the first filter, and the first filtering may be conducted therethrough. The pore size in this context may be referred to nominal values given by manufacturers of the filters. Various filters are commercially available from, for example, Nihon Pall Ltd., Advantec Toyo Kaisha Ltd., Nihon Entegris K.K. ( former ihon Mykrolis K . K . ) , and Kitz Micro Filter Corporation.

A second filter may be those composed of the same materials with the first filter described above.

The filtering through the first filter may handle the pigment dispersion only, and the second filtering may handle the colored radiation-sensitive composition obtained by mixing the resultant pigment dispersion with other components.

[0132] The colored radiation-sensitive composition of the present invention is suitable for various applications such as color filter for solid state imaging device, color filter for liquid crystal display device, printing ink, and inkjet ink.

[0133] <Colored Cured Film>

The colored cured film obtained by curing the coloring composition of the present invention is characterized by high color purity, large absorption coefficient even in the form of thin layer, and good fastness (in particular, heat resistance and light stability) . Since the colored cured film may give colored pixels with excellent hue, when observed on white LEDs used as a back light, so that an distinctive effect may be obtained when it is applied to liquid crystal display device provided with the white LED, and may be used for forming the colored pixels on the color filter for liquid crystal display device.

When the colored cured film is formed on an arbitrary substrate or base, the colored curable composition may be coated, or the substrate or the like may be dipped into the colored curable composition, to thereby form a colored curable composition layer, followed by curing. When a patterned colored cured film is formed, the colored curable composition may be applied by an inkjet recording process onto the substrate, or by publicly known printing process such as pattern printing or offset printing. From the viewpoint of possibility of forming a high definition pattern, a preferable method is such as forming a colored curable composition layer on a substrate, exposing the colored curable composition layer with light according to a predetermined pattern, and developing the colored curable composition layer so as to remove the unexposed portion, which will be described later.

[0134] <Processes for preparing color filters>

The color filters of the present invention use the curable colored compositions of the present invention described above. For example, they comprise a colored pattern of one or more colors (preferably three or four colors) using a curable colored composition of the present invention as described above on a substrate as described below.

The color filters of the present invention use the curable colored compositions of the present invention having a wide margin of DOF so that developer residues or pattern edge roughness can be reduced.

[0135] The thickness of the colored pattern here is preferably 0.1 μιτι to 2.0 μπι, more preferably 0.2 μπι to 1.0 μιη to form a finer pattern or to prevent adjacent image sensors from receiving light passing obliquely through the color filters.

[0136] The process for preparing the color filters of the present invention is not specifically limited. For example, a preferred process for preparing a color filter comprises the steps of applying a curable colored composition of the present invention as described above on a substrate, then exposing the applied coating layer through a mask, and developing the exposed coating layer to form a colored pattern. Color filters of 3 or 4 colors can be prepared by repeating these steps for each color to form a pattern of each color.

[0137] A more specific example of the process for preparing a color filter is explained below.

Thus, the process comprises the steps of applying a curable colored composition of the present invention on a substrate (preferably by coating) (optionally followed by a prebaking step for prebaking the applied curable colored composition); exposing the applied curable colored composition in a pattern through a mask; and developing the curable colored composition exposed in a pattern with an alkaline developer (optionally followed by a postbaking step for postbaking the curable colored composition developed with an alkaline developer) .

[0138] More specifically, the coating step comprises, for example, applying a curable colored composition of the present invention by a spinner or the like on a suitable substrate to provide a smooth coating layer typically having a thickness after drying of 0.1 μπι to 5 μιιι , preferably 0.2 μιτι to 2 ym.

[0139] After the curable colored composition is applied, it is typically prebaked to evaporate the solvent and thereby obtain a dried coating layer (prebaking step) . This prebaking takes place by indirect heat drying with hot air or the like, or direct heat drying on a hot plate or the like (at about 80 to 140 °C for 50 seconds to 200 seconds), etc. Prebaking may be preceded by vacuum drying.

Further, postbaking takes place to sufficiently cure the pattern obtained after development, thereby increasing its mechanical strength and giving a permanent film (postbaking step) . When a color filter of three colors is to be prepared, for example, the initially formed pattern subsequently undergoes two cycles of applying resist solutions of the other colors, and then development and exposure.

Postbaking is intended to prevent color mixture with the applied resist solutions and pattern missing due to exposure and development during these cycles. This postbaking takes place in the same manner as described for prebaking, but at higher temperatures for longer periods than prebaking conditions. For example, it involves indirect heating in an oven at about 180 to 250 °C for about 0.5 hours to 2 hours, or direct heating on a hot plate at about 180 to 250 °C for about 2 minutes to 10 minutes.

[0140] The light source for pattern exposure during the exposure step is not specifically limited. A preferred light source having a remarkable effect on patternability is light at a wavelength of 410 nm or less, especially preferably i-line (365 nm) from mercury lamps.

[0141] The developer used for developing the curable colored composition is not specifically limited, and previously known developers can be used. The developer is exemplified by organic alkaline compound aqueous ammonia, ethylamine, diethylamine , dimethyl ethanolamine,

tet ramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide,

tetrabutylammonium hydroxide, benzyl t rimethylammonium hydroxide, choline, pyrrole, piperidine,

1 , 8-diazabicyclo- [ 5 , , 0 ] -7-undecene . Among others, organic alkaline developers of quaternary ammonium salts such as tetramethyl ammonium hydroxide (TMAH) are preferred to achieve the object of the present invention.

[0142] The substrate is not specifically limited, and examples that can be used include glass substrates, plastic substrates, aluminum substrates, base materials for electronic components such as silicon wafers for

solid-state image sensors, transparent resin substrates, resin films, display surfaces of cathode-ray tubes, light-capturing surfaces of camera tubes, and semiconductor wafers on which solid-state image sensors (CCD, CMOS, BBD, CID, BASIS, etc.) have been formed. Further, contact image sensors using thin-film semiconductors, liquid crystal display surfaces, photoconductors for color

electrophotography, and elect rochromic (EC) display devices can also be used.

To improve adhesion to color filter layers, the substrate should preferably be subjected to high adhesion treatment. Specifically, a pattern of a curable colored composition may be formed after the substrate has been preliminarily coated with a thin layer of a silane coupling agent or the like or a silane coupling agent may be preliminarily contained in a curable colored composition.

[0143] When a step exists on the substrate, a curable colored composition of the present invention can be applied after a planarizing layer for removing the step to smooth the coating surface has been applied on the substrate. For example, solid-state image sensors such as CCD and CMOS comprise an optoelectronic converter zone (photodiode) for generating electrons on a silicon substrate depending on the amount of light received and a readout gate zone for outputting the generated electrons. A step may occur between the readout gate zone and the photodiode zone because a light-shielding layer is formed on the top of the readout gate zone to protect the readout gate zone against light, which otherwise would cause noises to hinder exact data output, while the photodiode zone has no light-shielding layer. If a color resist is applied on such a step to directly form a color filter, the optical path length increases, resulting in dark images and poor light gathering ability. To improve this, a transparent planarizing layer is preferably formed between a device such as CCD or CMOS and a color filter for the purpose of removing the step. Materials for this planarizing layer include photocurable resist solutions such as the curable colored compositions of the present invention and heat-curable resins such as acrylic resins and epoxy resins.

[0144] The colored cured film obtained by the method of manufacturing the color filter of the present invention, or, the color filter having the colored cured film formed by using the coloring composition of the present invention (color filter of the present invention) can provide vivid color and high contrast when images are displayed

therethrough, and are excellent in fastness (in particular, heat resistance and light stability) , since the coloring composition of the present invention is used therein. In addition, as will be described later, an excellent effect of reproducing good hues may be obtained, not only when a publicly- known CCFL is used as the back light, but also when white LEDs are used.

The color filter of the present invention are applicable to liquid crystal display devices and solid state imaging devices, and in particular suitable for the liquid crystal display devices. The liquid crystal display devices, applied with the color filter containing dyes as the colorant, is now capable of displaying images with excellent hues, spectral characteristics and contrast, and is well adapted to white LEDs .

[0145] While the applications of the coloring composition of the present invention has been described above, centered round formation of the colored pattern of the color filter, the coloring composition is also applicable to formation of a black matrix, which partitions the colored pattern (pixels) composing the color filter.

The black matrix on the substrate may be formed by using a colored curable composition which contains a processed pigment of black pigment such as carbon black or titanium black, and by the individual steps of coating, exposure, development, and optional post-baking.

[0146] The coloring layer, formed by applying the coloring composition of the present invention onto the substrate, preferably has a dry thickness of 0.3 pm to 5.0 μιη in general, more preferably 0.5 μιη to 3.5 μπι, and particularly 1.0 ym to 2.5 rn.

[0147] The color filter of the present invention obtained as described above configures the pixels together with G (green) and B (blue) color filters according to any of publicly known methods. The filter has a very high transparency, excellent in spectral characteristics, small in depolarization, and can therefore provide a liquid crystal display device capable of showing clear images. A device having the color filter formed therein can also provide a camera module having good spectral

characteristics.

The color filter of the present invention is also adoptable to liquid crystal display element, and solid state imaging devices such as CCD and CMOS (including organic CMOS), and is suitable for a high-definition CCD element and CMOS element having the number of pixels exceeding 1,000,000.

[0148] The color filter of the present invention is adoptable to liquid crystal display element and solid state imaging device, and is particularly suitable for the liquid crystal display element. The liquid crystal display element applied with the color filter is less likely to cause alignment failure of liquid crystal molecules due to lowered specific resistance, even under the presence of a metal complex dye, as a colorant, excellent in spectral characteristics and heat resistance, and is therefore excellent in hue of displayed images and display

characteristics .

[0149] <Liquid Crystal Display Element>

The color filter of the present invention, characterized by its colored pixels with excellent hue and light stability, is particularly suitable for use in the liquid crystal display device. The liquid crystal display element applied with the color filter can show high quality images with good hue of displayed images and excellent display

characteristics .

[0150] Definition of display devices and details of the individual display devices are described, for example, in "Denshi Disupurei Debaisu (in Japanese) (Electronic Display Device) , written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990", "Disupurei Debaisu (Display Device) by Sumiaki Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989)" and the like. Liquid crystal display devices are described, for example, in "Jisedai Ekisho Disupurei Gijutu (in Japanese) (Next-Generation Liquid Crystal Display

Technology), edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable may be any of those of various types described, for example, in "Jisedai Ekisho Disupurei Gijutu (in Japanese)

(Next-Generation Liquid Crystal Display Technology) mentioned above, without special limitation.

[0151] The color filter of the present invention is particularly effective in color TFT liquid crystal display device. The color TFT liquid crystal display device is described, for example, in "Kara TFT Ekisho Disupurei (in Japanese) (Color TFT Liquid Crystal Display) (Kyoritsu Shuppan Co., Ltd., 1996)". The present invention is also applicable to liquid crystal display devices with wider viewing angles such as those based on in-plane switching (IPS) system or a multi-domain vertical alignment (MVA) system, or STN, TN, VA, OCS, FFS and R-OCB.

The color filter of the present invention is also applicable to COA (Color-filter On Array) system characterized by high brightness and high definition. In the COA type liquid crystal display device, the color filter layer may be necessary to satisfy, in addition to general requirements described above, requirements on interlayer insulating film such as low dielectric constant and resistance to a removing liquid. The color filter of the present invention is obtained by curing the composition of the present invention, and this supposedly contributes to strongly prevent the specific resistance of the liquid crystal molecules from lowering, and thereby to prevent alignment failure of the liquid crystal molecules, that is, degradation in display characteristics. Accordingly, good color purity and hue are ensured, and thereby the COA-type liquid crystal display device with high resolution and good long-term durability may be provided. In order to satisfy a requirement to lower the dielectric constant, the color filter layer may be overlaid with a resin coating.

For the colored layer used in the COA-type device, it is necessary to form a conduction path in the form of rectangular throughholes having an edge of approximately 1 to 15 μηα long, or dips having a shape in which one side removed from a square, through which ITO electrodes disposed over the coloring layer and terminals of a driving substrate below the coloring layer are electrically connected . A size of the conduction path (or, length of edge) of 5 pm is particularly preferable, and this is successfully achieved by the present invention. These modes of image display are described, for example, in "EL, PDP, LCD Disupurei - Gijutsu to Shijo no Saishin Doko- (in Japanese) (EL, PDP, LCD Displays -The Latest Trends of Technology and Market) (Research Study Division of Toray Research Center, Inc. , 2001)", p.43. [0152] The liquid crystal display device of the present invention is configured by the color filter of the present invention, and also by various components such as substrate with electrodes, polarizer film, phase difference film, back light, spacer, and view angle compensation film. The color filter of the present invention is adoptable to a liquid crystal display device configured by these

publicly-known components. These components are described, for example, in "'94 Ekisho Disupurei Shuuhen Zairyo* Kemikaruzu no Shijo (in Japanese) ('94 Market of Liquid Crystal Display Related Materials and Chemicals), (by Kentaro Shima, CMC Publishing CO., LTD., 1994)" and "2003 Ekisho Kannren Shijo no Genjo to Shorai Tenbou (in Japanese) (Current Status and Future Prospects of Liquid Crystal Related Market (by Ryokichi Omote, Fuji Chimera Research Institute, Inc., 2003)".

The back light is described, for example, in SID meeting Digest 1380 (2005) (A. Konno et al.) and Gekkann Disupurei

(in Japanese) (Monthly Display, 2005 December, p.18-24 (by Hiroyasu Shima), and p.25-30 (by Takaaki Yagi) .

[0153] The color filter of the present invention can achieve high contrast, when incorporated into the liquid crystal display element, and when combined with a

publicly-known, three-wavelength cold cathode tube. By using red, green and blue LEDs (RGB-LED) as the backlight, the liquid crystal display device may further be improved in luminance, color purity, and color reproducibility.

[0154] <Solid State Imaging Device>

The solid-state imaging device of the present invention has the above-described color filter for solid-state imaging device of the present invention. The configuration of the solid-state imaging device of the present invention is not specifically limited so long as the device has the color filter for solid-state imaging device of the present invention, and can function as a solid-state imaging device. An exemplary configuration is as follows.

[0155] The configuration is such as having, on a support, a plurality of photodiodes which configure a light-receiving area of the solid-state imaging device (e.g., CCD image sensor, CMOS image sensor), and transfer electrodes composed of polysilicon or the like; a light-shielding film composed of tungsten or the like, formed over the photodiodes and the transfer electrodes so as to expose only the light-receiving section configured by the photodiodes; a device protective film composed of silicon nitride or the like, formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving section configured by the photodiodes; and the color filter for solid-state imaging device of the present invention formed on the device protective film.

Other possible configurations include a configuration having a light condensing unit (for example, a microlens, the same will apply also hereinafter) on the above-described device protective layer and below the color filter (more closer to the support), and a configuration having a light condensing unit on the color filter.

EXAMPLES

[0156] The present invention will further be detailed below referring to Examples. Materials, amount of use, ratio, details of processes, procedures of process and so forth described in Examples below may be modified arbitrarily, without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed to be limited by Examples below. In Examples, wording of "part (s) " used for describing the amount of use means "part (s) by weight", unless otherwise specifically stated .

[0157] (Synthesis example 1)

Synthesis of compound (I-a)

Compound (I-a) was synthesized according to the scheme shown below.

[0158] <Synthesis of compounds (3) and (4)>

A mixture of 100 g of compound (1) in 200 mL of methanol was stirred at 0 °C. To the mixed solution was added dropwise a solution of 124 g of compound (2) in 100 mL of methanol while maintaining the internal temperature at 10 °C or less. Then, the reaction temperature was raised to room temperature, and the mixture was stirred for 30 minutes. A solution of 96.6 g of hydroxylamine hydrochloride in 200 mL of methanol was neutralized by adding 268 g of a 28 % solution of sodium methoxide in methanol, and the precipitated salt was removed and the resulting solution was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 6 hours. After the solvent was distilled off, the mixture was cooled to 0 °C, and the precipitated crystals were filtered to give 120 g of compound (4) .

[0159] <Synthesis of compounds (5) and (6)>

A solution of 200 g of compound (4) in 600 mL of

N , -dimethylacetamide was stirred at 0 °C, and 191 g of p-toluenesuofonyl chloride was added in four portions while maintaining the internal temperature at 10 ° C or less, and the mixture was stirred at 0 °C for 30 minutes. To this was added dropwise 103 g of pyridine while maintaining the internal temperature at 10 °C or less, and the mixture was further stirred for 1 hour and a half. This reaction solution was poured into water (1.5 L) with ice-cooling, and the precipitated crystals were filtered to give compound (5). In a stirred mixture of the resulting compound (5) in 1 L of methanol was added 103 g of pyridine. The reaction solution was heated under reflux for 1 hour, and then cooled to 0 °C, and the resulting crystals were filtered to give

92 g of compound (6) .

[0160] <Synthesis of compound (7)>

A mixture of 200 g of compound (6) in 2.6 L of acetic acid was stirred at room temperature. To this was added dropwise 392 g of triethyl orthoformate , and the mixture was stirred at 85 °C for 2 hours. Then, the mixture was cooled to room temperature, and 1.3 L of methanol was added dropwise, and the resulting crystals were filtered to give 200 g of compound (7).

[0161] <Synthesis of compound (I-a)>

A mixture of 220 g of compound (7), 1.5 L of tetrahydrofuran, and 1.5 L of N-methylpyrrolidone was stirred at room temperature. To this was added 170 g of zinc acetate dihydrate, and the mixture was stirred at 70 °C for 2 hours. Then, the mixture was cooled to room temperature, and the resulting solid was filtered to give 220 g of compound (I-a) .

[0162] (Synthesis examples 2 to 4)

Synthesis of compounds (I-b), (I-d), and (I-h)

These compounds were synthesized in the same manner as described for compound (I-a) .

[0163] (Synthesis example 2)

Synthesis of compound (I-k)

Compound (I-k) was synthesized according to the scheme shown below.

[0164] <Synthesis of compound (8)>

To dimethyl formamide (15 mL) stirred at 0 °C was added dropwise phosphorus oxychloride (11.3 g) while maintaining the internal temperature at 5 °C or less, and the mixture was stirred at 0 °C for 1 hour to prepare a formylating agent. To a solution of compound (6) (10 g) dissolved in dimethyl formamide (30 mL ) and stirred at 0 °C was added dropwise the formylating agent while maintaining the internal temperature at 5 °C or less, and the mixture was stirred at 0 °C for 1 hour. Then, the reaction temperature was raised to room temperature, and the mixture was further stirred for 1 hour. The reaction solution was extracted with and partitioned between water (50 mL) and ethyl acetate (50 mL) . The resulting organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution (50 mL) and separated. The solvent was distilled off under reduced pressure from the resulting organic layer to give a white solid. To this white solid was added acetone (50 mL) , and the mixture was stirred and the solid was filtered to give compound (8) (7 g) .

[0165] <Synthesis of compound (9)>

Com ound (9) was synthesized through the route shown below.

[0166] <Synthesis of compound (9b)>

A solution of 90.8 g of ethyl isonicotinate (9a) and 24.6 g of acetonitrile dissolved in 500 mL of toluene was stirred at 0 °C. To this mixed solution was added 74.1 g of potas s ium t-butoxide while maintaining the internal temperature at 5 °C or less. Then, the reaction temperature was raised to room temperature, and the mixture was stirred for 1 hour. To the reaction solution was added 100 mL of toluene, and the precipitated crystals were filtered to give 89.1 g of compound ( 9b ) .

[0167] <Synthesis of compound (9c)> To a mixture of 95 g of compound (9b) in 500 mL of ethanol was added 35.3 g of hydrazine hydrochloride at room temperature, and the mixture was stirred. The mixture was heated under reflux at 85 °C for 7 hours, and the reaction solution was cooled to room temperature. To the reaction solution was added dropwise 100 mL of hydrochloric acid, and the precipitated crystals were filtered to give 152.9 g of compound (9c) .

[0168] The subsequent procedures were performed in the same manner as described for compound (6) by using this compound (9c) as a starting material in place of compound (1) to synthesize compound (9) .

[0169] <Synthesis of compound (10)>

A mixture of compound (8) (5 g) and compound (9) (5.2 g) in methanol (15 mL) was stirred. To this was added dropwise acetic acid (15 mL) and the mixture was heated under reflux at 70 °C for 3 hours. The reaction solution was cooloed to room temperature and the crystals were filtered to give compound (10) (8 g) .

[0170] <Synthesis of compound (I-k)>

A mixture of 5 g of compound (10) , tet rahydrofuran (25 mL) and N-methylpyrrolidone (25 mL ) was stirred at room temperature. To this was added zinc acetate dihydrate (1.6 g) , and the mixture was stirred at 70 °C for 2 hours. Then, the mixture was cooled to room temperature and the resulting solid was filtered to give compound (I-k) (3.5 g) .

[0171] (Evaluation)

The compounds synthesized in Synthesis examples 1 to 4 were evaluated for heat resistance and volatility according to the criteria described below.

[0172] <Heat resistance>

Each compound obtained was heated from 40 °C to 600 °C at 10 °C/min in a TG/DTA analyzer (EXSTAR 6000 from SII NanoTechnology Inc. (current Hitachi High-Tech Science Corporation) ) to determine its decomposition temperature. Evaluation was based on the following criteria.

: the compound decomposes above 300 °C, or never decompose s . B: the compound decomposes at or below 300 °C and above 200 °C.

C: the compound decomposes at or below 200 °C.

[0173] <Volatility>

Each compound obtained was heated from 40 °C to 600 °C at 10 °C/min in a TG/DTA analyzer (EXSTAR 6 000 from SII NanoTechnology Inc. (current Hitachi High-Tech Science Corporation) ) to determine its weight loss. Evaluation was based on the following criteria.

A: weight loss of less than 10 % at or below 400 °C.

B: weight loss of 10 % or more and less than 30 % at or below 400 °C.

C: weight loss of 30 % or more at or below 400 °C.

[0174] <Solvent resistance>

Each compound obtained was evaluated by the method described in the section of resistance to solvent bleeding in JIS K 5101-1991 15.

[0175] The following compounds were used as comparative examples and evaluated for heat resistance and volatility in the same manner as described for the compounds synthesized in Synthesis examples 1 to 4.

[0176] Comparative compound A: the compound of an example

[0177] Comparative compound B: the compound of an example described in Japanese Patent No. 3750208.

Comparative compound C: Methine colorant which is Zn non-compl exat ion compound of compound (1-a) (Compound 7) [0178]

[Table 1] Heat Solvent Molecular

Compound Volatility

Resistance Resistance Weiaht

Example 1 (l-a) A A Grade 5 627.97

Example 2 (l-b) A A Grade 5 876.25

Example 3 (l-d) A A Grade 5 993.35

Example 4 (l-h) A A Grade 5 880.20

Example 5 (l-k) A A Grade 5 754.09

Example 6 (H) A A Grade 4 752.11

Example 7 (l-m) A A Grade 5 856.84

Comparative Comparative

C C Grade 4 907.75 Example 1 Compound A

Comparative Comparative

B A Grade 3 601.14 Example 2 Compound B

Comparative Comparative

C C Grade 2 282.30 Example 3 Compound C

[0179] The table shows that the compounds of Examples are excellent in heat resistance and volatility. However,

Comparative examples 1 to 3 are shown to be poor in at least one of heat resistance and volatility.

[0180] (Example 101: Preparation of a color filter)

<Preparation of a resist solution for a planarizing layer>

The following components were mixed in a stirrer to prepare a resist solution for a planarizing layer.

[Components of a resist solution for a planarizing layer]

- Benzyl methacrylate/methacrylic acid copolymer (=70/30 [in molar ratio] ) 16.4 parts by weight

- Dipentaerythritol pentaacrylate 6.5 parts by weight

- Propylene glycol monomethyl ether acetate

13.8 parts by weight

- Ethyl 3 -ethoxypropionate 12.3 parts by weight

- Triazine initiator shown below 0.3 parts by weight

[0181] <Preparation of a planarized wafer>

The resist solution for a planarizing layer obtained above was uniformly applied on a 6-inch silicon wafer by spin-coating to form a coating layer, and the resulting coating layer was heated on a hot plate at a surface temperature of 120 °C for 120 seconds. The spin coating speed here was controlled to give a coating layer having a thickness of about 1 pm after the heat treatment.

After the heat treatment, the coating layer was further treated in an oven at 220 °C for 1 hour, whereby the coating layer was cured to form a planarizing layer.

This gave a planarized wafer having a planarizing layer formed on the 6-inch silicon wafer.

[0182] <Preparation of a color resist solution (a curable colored composition) >

The following components were mixed in a stirrer to prepare a color resist solution.

[Components of a color resist solution]

- Benzyl methacrylate / methacrylic acid copolymer (=70/30 [in molar ratio]) 3.27 parts by weight

- Compound (I-h) 6.65 parts by weight

- Polymeric dispersant (a pigment dispersant available from BYK Chemie under Disperbyk 170) 2.56 parts by weight

- Propylene glycol monomethyl ether acetate

81 parts by weight

- IRGACURE OXE01 (photoinit iator from BASF)

1.65 parts by weight - p-Methoxyphenol (polymerization inhibitor)

0.002 parts by weight

- ARONIX M-305 (polymeri zable compound from Toagosei Co., Ltd.) 1.47 parts by weight

- Polymerizable compound shown below 3.42 parts by weight

(All (n) s add up to 12 ) [0183] <Preparation of a color filter>

The color resist solution obtained above was uniformly applied on the planarizing layer of the planarized wafer by spin-coating to form a coating layer, and the resulting coating layer was heated (prebaked) on a hot plate at a surface temperature of 100 °C for 120 seconds to form a color resist layer. The spin coating speed here was controlled to give a coating layer having a thickness of about 0.8 μπι after the heat treatment .

[0184] Then, the color resist layer was exposed in a pattern through the photomask described below by using an i-line stepper (FPA-3000i5+ from Canon, Inc.).

The pattern exposure was performed in the form of a matrix having 21 rows and 19 columns in a total of 399 cells. Conditions were selected to increment the exposure dose by 250 J/m ² in each successive one of the 21 rows starting from the minimum exposure dose of 500 J/m ² .

Conditions were also selected to allow the focal length to vary by 0.1 pm in each successive one of the 19 columns starting from the optimal focal length (Focus 0.0 pm) assigned to the center. Specifically, the focal length varies in each successive column starting from the optimal focal length assigned to the center column.

The photomask used was a photomask having a mask pattern in which square pixel patterns of six sizes (1.0 pm square, 1.5 pm square, 2.0 pm square, 3.0 m square, 4.0 pm square, and 7.0 pm square) are arrayed in an area of 4 mm x 3 mm.

[0185] The color resist layer exposed in a pattern was developed by the Puddle method using the organic alkaline developer CD-2060 (from FUJIFILM Electronic Materials Co., Ltd. ) at room temperature for 60 minutes. This was followed by spin shower rinsing with pure water for 20 seconds and further washing with pure water. Then, water drops were removed by high-pressure air and the substrate was air-dried to give a colored pattern. Thus, a color filter was obtained .

[0186] This color filter was used in a solid-state image sensor and a liquid crystal display device to show that both exhibited excellent performance.

[0187]

The present disclosure relates to the subject matter contained in Japanese Patent Application No. 217501/2012 filed on September 28, 2012, which is expressly incorporated herein by reference in their entirety. All the publications referred to in the present specification are also expressly incorporated herein by reference in their entirety.

The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.