TW201425485A - Pigment, pigment dispersion, colored composition, curable colored composition, radiation-sensitive colored composition, color filter, ink, solid-state imaging sensor, liquid crystal display device, and process for preparing color filter - Google Patents

Abstract

Provided are 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. A pigment represented by formula (I): In formula (I), R1 to R4 each independently represent alkyl, aryl, heterocyclyl, alkoxycarbonyl, carbamoyl, alkoxy, amino, a group forming a sulfonamide, a sulfonic acid ester or a sulfone, or cyano; R5 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.

Description

Pigment, pigment dispersant, color composition and color filter using the same

The present invention relates to a pigment, a compound constituting a pigment, a pigment dispersant, a color composition, a curable color composition, a color resist liquid, a color filter, an ink for inkjet printing, and a feeling of using the same A method of producing a linear color composition.

Since a small-sized liquid crystal display device and an organic electro-display device of a mobile phone, a mobile game machine, a PDA, etc. must use a backlight powered by a secondary battery or a dry battery having a limited capacitance, it is possible to efficiently The colorant that the backlight transmits the wavelength of the bright line to display a high-brightness color image has been advantageously used as the color material of the color filter of these display devices.

In recent years, the size of liquid crystal display devices and organic electroluminescent display devices (which are directly applied to displays such as personal computers and televisions) has been increased. The color reproducibility of crystal display devices and organic electrodisplay devices has received great attention. For those liquid crystal display devices and organic electroluminescent display devices that are used outdoors, heat resistance and volatility have also received great attention.

Regarding the coloring material for a color filter, for example, Patent Document 1 proposes a coloring material including a metal chelate dye having a specific structure of a symmetric methine dye, and Patent Document 2 proposes a colorant of a mixture of any of the following specific structures and a metal ion-containing compound, the dye of the specific structure described above being a symmetric methine dye, a polymethine dye, and a squarylium dye. . Further, for another example, Patent Document 3 proposes a metal complex dye which is formed of a methine dye or an azomethine dye and a metal, and Patent Document 4 proposes a color of a dye including a specific structure. material.

[references] [Patent Document]

Patent Document 1: JP-A2007-100061

Patent Document 2: JP-A 2001-342364

Patent Document 3: JP-A-H9-143382

Patent Document 4: JP-A2005-250420

However, it has been found that in Patent Document 1, the heat resistance, volatility and solvent of the dye are present because the methine dye exists in the form of a neutral ligand. The solvent resistance is insufficient. Further, the dye having the structure described in Patent Document 2 or Patent Document 3 is inferior in properties such as heat resistance. The present invention overcomes the above disadvantages and provides a pigment having excellent heat resistance and volatility, a compound constituting the pigment, and a pigment composition, a color composition, a curable color composition, a color filter, and an inkjet printing. Ink and a method of producing a radiation-sensitive color composition using the same.

In order to solve the above problems, after careful study, the above problems can be solved by using a pigment including a metal complex of a methine dye having a specific structure.

The technical means for solving the above problems are shown in the following [1], and are preferably the following [2] to [20].

[1] A pigment represented by the formula (I): In the formula (I), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate. a sulfonic acid ester or a hydrazine group or a cyano group; R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; M represents a monovalent to trivalent metal; and L represents an anion capable of coordinating to a metal or The ligand; 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 a whole group.

[2] The dye according to [1], wherein, in the above formula (I), R ³ and R ⁴ each independently represent an alkyl group having 1 to 5 carbon atoms.

[3] The dye according to [1] or [2] wherein, in the above formula (I), R ¹ and R ² each independently represent an alkyl group, an aryl group or a heterocyclic group.

[4] The dye according to [1] to [3] wherein, in the above formula (I), R ^l and R ² are the same group, and R ³ and R ⁴ are the same group.

[5] The pigment according to [1] to [4], wherein the pigment has a grade 5 anti-solvent exudability according to an absolute comparison method of JIS K 5101-1991 15 ( Effective bleeding.

[6] The dye according to [1] to [5], wherein in the above formula (I), n is 0.

[7] The dye according to [1] to [6], wherein the compound represented by the above formula (I) is a compound represented by the following formula (IA): In the formula (IA), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; each of R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and M' represents a divalent metal atom; the groups included in the parentheses each form a monovalent anion as a whole group .

[8] The dye according to [1] to [7], wherein M in the above formula (I) and M' in the above formula (I-A) represent zinc.

[9] The dye according to [1] to [8], wherein the compound represented by the above formula (I) is any one of the compounds represented by the following formulas (Ia) to (In):

In the formula (I-f) and the formula (I-1), Me represents a methyl group.

[10] The dye according to [1] to [9], wherein the compound represented by the above formula (I) has a molecular weight of 500 to 1200.

[11] A pigment dispersion comprising at least one of the pigments according to any one of [1] to [10].

[12] A colored composition comprising at least one of the pigments according to any one of [1] to [10].

[13] A curable color composition comprising at least one of the pigments according to any one of [1] to [10].

[14] A radiation-sensitive color composition comprising at least one of the pigments according to any one of [1] to [10].

[15] A color filter formed by using the curable color composition as described in [13].

[16] An ink for inkjet printing using the color composition as described in [12].

[17] A solid-state image sensor or a liquid crystal display device comprising the color filter according to [15].

[18] A method of producing a color filter, comprising: applying a curable color composition as described in [13] onto a substrate; and applying the curable color composition to the pattern via a mask Medium exposure; and development of the curable color composition exposed to the pattern using an alkaline developer.

[19] A composition comprising a compound represented by the formula (I), wherein, in the composition, the compound represented by the formula (I) accounts for 50% by mass or more:

In the formula (I), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; M represents a monovalent to trivalent metal; L represents an anion or a ligand capable of coordinating to a metal; m represents 1 to An integer of 3; and n represents an integer from 0 to 2; the group included in the parentheses forms a monovalent anion as a unitary group.

[20] The composition according to [19], wherein the compound represented by the above formula (I) is a compound represented by the following formula (IA): In the formula (IA), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; each of R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and M' represents a divalent metal atom; the groups included in the parentheses each form a monovalent anion as a whole group .

According to the present invention, a dye having excellent heat resistance and volatility, a compound constituting a pigment, and a pigment composition, a color composition, a curable color composition, a color filter, an ink for inkjet printing, and the like can be provided. A method of producing a radiation sensitive color composition using them.

The contents of the present invention will be described in detail below. In this document, the range of numbers expressed by "to" refers to the range of numbers expressed by the numbers preceding "to" and the following numbers, which are used as the lower and upper limits, respectively.

As used herein, the term "radiation" includes visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. As used herein, the term "colored layer" refers to a film layer composed of pixels and/or black matrix used in a color filter.

Further, as used herein, the term "pigment" means a compound which is hardly soluble in water and an organic solvent, and is preferably evaluated according to the absolute comparison method of JIS K 5101-1991 15. The compound of the 5-stage anti-solvent exudation property is more preferably a compound having the anti-solvent exudation property of the 5th grade or higher. More specifically, it is evaluated according to the standard described in the "Organic Pigment Handbook" edited by Color Office, page 363, and "pigment" means a compound evaluated as the fifth stage.

(pigment)

The pigment of the present invention is characterized in that it is represented by the formula (I). The present invention also provides a composition comprising the compound represented by the formula (I), characterized in that it is composed here The compound represented by the formula (I) accounts for 50% by mass or more, or even 80% by mass of the colorant of the composition.

In the formula (I), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; M represents a monovalent to trivalent metal; L represents an anion or a ligand capable of coordinating to a metal; m represents 1 to An integer of 3; and n represents an integer from 0 to 2; the group included in the parentheses forms a monovalent anion as a unitary group.

R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an amine carbenyl group, an alkoxy group, an amine group, a group forming a sulfonamide, a sulfonate or an anthracene or a cyano group. .

Preferably, the alkyl groups are each an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be straight chain, branched or cyclic, and the alkyl group may be further substituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group, a thirteen group, and a hexadecyl group , octadecyl, hexyl, isopropyl, isobutyl, s-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2 -ethylhexyl, 2-methylhexyl, Cyclohexyl, cyclopentyl, 2-norbornyl and the like. Among these groups, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, and a third butyl group are preferred, and a methyl group is more preferred.

The substituent which may be present on the alkyl group includes an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a halogen atom (a fluorine atom) , chlorine atom, bromine atom, iodine atom).

Preferably, the aryl group is an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. The aryl group can be further substituted. Specific examples of the aryl group include a phenyl group, a p-tolyl group, a naphthyl group, an onion group, and the like. The substituent which may be present on the aryl group is the same as the substituent which may be present on the alkyl group. Among these groups, preferred are phenyl, p-methoxyphenyl, o-methoxyphenyl, p-chlorophenyl and o-chlorophenyl, more preferably p-methoxyphenyl, o-methoxyphenyl, P-chlorophenyl and o-chlorophenyl.

Preferably, the heterocyclic group is a heterocyclic group having 6 to 30 carbon atoms, more preferably a heterocyclic group having 6 to 14 carbon atoms, and particularly preferably a heterocyclic ring having 6 to 10 carbon atoms. base. The heterocyclic group can be further substituted. Specific examples of the heterocyclic group include pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, thiazolyl, and benzo-fused ring systems thereof and Among the groups, a cyclocondensate ring system or the like is preferably a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a pyridyl group, and a pyrimidinyl group, and more preferably a pyridyl group.

Preferably, the alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 30 carbon atoms, more preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and particularly preferably 1 to 1 An alkoxycarbonyl group of 6 carbon atoms. The alkoxycarbonyl group may be linear, branched or cyclic, and the alkoxycarbonyl group may be further substituted. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, an n-octadecyl oxycarbonyl group, and the like. Among these groups, a methoxycarbonyl group and a methoxycarbonyl group are preferred. Tributyloxycarbonyl. The substituent which may be present on the alkoxycarbonyl group is the same as the substituent which may be present on the alkyl group.

Preferably, the amine carbenyl group is an amine carbenyl group having 0 to 30 carbon atoms, more preferably an amine carbenyl group having 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms. Aminomethyl thiol. The amine carbenyl group may be linear, branched or cyclic, and the amine carbenyl group may be further substituted. Specific examples of the amine methyl sulfhydryl group include an amine methyl sulfhydryl group, an N-methylamine methyl fluorenyl group, an N,N-dimethylamine carbhydryl group, an N,N-di-n-octylamine fluorenyl group, and N- Among these groups, an aminomethyl sulfhydryl group and an N-methylamine fluorenyl group are preferred. Substituents which may be present on the amine carbenyl group are the same as those which may be present on the alkyl group.

Preferably, the alkoxy groups are each an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and particularly preferably an alkane having 1 to 3 carbon atoms. Oxygen. The alkoxy group may be linear, branched or cyclic, and the alkoxy group may be further substituted. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a third butoxy group and the like. Among these groups, a methoxy group and a preferred group are preferred. Oxygen. The substituent which may be present on the alkoxy group is the same as the substituent which may be present on the alkyl group.

The amine group may be substituted or preferably unsubstituted. Examples of the group forming a sulfonamide, sulfonate or oxime include an alkoxysulfonyl (preferably An alkoxysulfonyl group having 1 to 3 carbon atoms, an aryloxysulfonyl group (preferably an aryloxysulfonyl group having 6 to 8 carbon atoms), an alkylsulfonyl group (preferably) An alkylsulfonyl group having 1 to 3 carbon atoms, an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 8 carbon atoms), and optionally an alkyl group on the nitrogen atom Or an aryl-substituted aminosulfonyl group (preferably an aminosulfonyl group optionally substituted on the nitrogen atom by an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 8 carbon atoms) ).

Wherein R ¹ and R ² each independently represent an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group or a heterocyclic group. More specifically, a methyl group, a p-methoxyphenyl group, an o-methoxyphenyl group, a p-chlorophenyl group, an o-chlorophenyl group, and a pyridyl group are preferred.

R ³ and R ⁴ each independently represent an alkyl group, an aryl group or a heterocyclic group, more preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group. R ³ and R ^{4 are} preferably the same group, and R ¹ and R ^{2 are} also the same group. The symmetrical compound represented by the formula (I) has the advantages of obtaining desired absorption characteristics (bluish tint) and ease of preparation. The symmetrical compound represented by the formula (I) also has an advantage that the association is improved, so that it can be easily converted into a pigment.

R ⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The alkyl group, the aryl group or the heterocyclic group represented by R ^{5 has the same} meaning as the alkyl group, the aryl group or the heterocyclic group represented by R ¹ to R ⁴ , and a similar preferred range is also encompassed. Preferably, R ⁵ is a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

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

L represents an anion or a ligand capable of coordinating to a metal. The ligand is not particularly limited as long as it can be coordinated to M in the formula (I), but the ligand preferably has a substituent containing C, N, O or S, and more preferably has a lone pair A group of electrons (such as N, O or S). The compound forming the ligand includes a carboxylate, a carbonyl (ester, a ketone), a phosphate, a sulfonate, an amine, a guanamine, a sulfonamide, a urethane, A compound of urea, an alcohol, a thiol or the like, preferably a compound having a carboxylate, a carbonyl (ester, ketone), a phosphate, a sulfonate or an amine, more preferably a carboxylate or a carbonyl group ( A compound of an ester, a ketone, a phosphate or an amine. The number of the coordinating groups contained in the molecule is not limited to one, but may be two or more, and the coordinating group may be dissociated or undissociated. Examples of the anion capable of coordinating to a metal include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF ₆ and BPh ₄ , wherein Ph represents a phenyl group. .

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.

Formula (I) forms a monovalent anion as an integral group included in the parentheses. Primarily, the six nitrogen atoms together form a monovalent anion, but a carbon atom or substituent or analog thereof can contribute to the formation of an anion. In other words, the formula (I) has a structure in which a group included in the parentheses forms a coordinate bond and/or an ionic bond with M (monovalent to trivalent metal).

Preferably, the compound represented by the formula (I) is a compound represented by the formula (IA):

In the formula (IA), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; each of R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and M' represents a divalent metal atom; the groups included in the parentheses each form a monovalent anion as a whole group .

In formula (IA), R ¹ to R ⁴ and R in formula (I) ¹ to R ⁴ are synonymous Qieyi covers similar preferred ranges.

In formula (IA), R ^{5 is} synonymous with R ⁵ in formula (I) and encompasses similar preferred ranges.

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

Preferably, the compound represented by the formula (I) has a molecular weight of from 500 to 1200, preferably from 500 to 1,000, still more preferably from 500 to 900. When the molecular weight is from 500 to 1200, the hue and volatility approach are improved.

Preferably, the compound represented by the formula (I) has a mass of each of R ³ and R ⁴ per molecule of from 2 to 200, preferably from 2 to 150, particularly preferably from 12 to 80. Such a structure tends to provide a compound of higher purity.

Specific examples of the compound represented by the formula (I) are shown below. In the following formula, Me represents a methyl group. When the Zn of the compound of the following formula is substituted by Be, Mg, Ca, Ba or Cd, it is also preferred to use the compound as the compound of the present invention.

Among the compounds represented by the formula (I-a) to the formula (I-n), preferred are the compounds represented by the formula (I-a) to the formula (I-1).

The compound represented by the formula (I) can be synthesized based on a conventional method. For example The exemplary compound (I-a) can be synthesized according to the scheme shown below.

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

Preferably, the dye of the present invention comprises a compound represented by the formula (I), and the compound has a solvent-leaking property of the fifth grade, which is evaluated according to the absolute comparison method of JIS K 5101-1991 15. Preferably, when the color tone is represented by λ _max , the compound represented by the formula (I) has a λ _{max of} from 420 to 470, more preferably λ _{max of} from 430 to 465, still more preferably λ _{max of} from 440 to 460.

Preferably, the color composition of the present invention comprises a colorant, and the main component contained in the colorant is a compound represented by the formula (I). The term "principal component" means the component included in the highest content among the included blue colorants. Examples of the color composition of the present invention include a radiation-sensitive color composition for a color resist solution and the like, and an ink for inkjet printing.

A method of converting a compound of the present invention into a pigment includes: removing a soluble group; introducing a hydrogen-bonding group into the molecule to increase intramolecular and intermolecular hydrogen bonding strength; A substituent of an electronic system or an analog thereof is introduced into the molecule to increase the intermolecular Π-Π stacking strength and the like. In addition, this will Other useful methods for converting the compound of the invention into a pigment include: polymerizing the compound; enhancing the intermolecular force by the force of the halogen or the like.

Soluble groups include long chain alkyl and alkenyl groups containing six or more carbon atoms and analogs thereof. For example, a hydrogen bonding group includes a hydroxyl group, a mercapto group, an alkoxy group, a thioalkoxy group, an amine group, a carbamate, a guanamine, a sulfonamide, a urea group, a thiourea group, Phosphate and the like. The substituent of the oxime-electron system includes a substituent containing an unsaturated bond, a substituted or unsubstituted aryl group, an aromatic heterocyclic group or the like.

(pigment dispersant)

The pigment dispersant of the present invention is characterized in that it comprises at least one of the above-mentioned pigments. This allows the pigment dispersant to provide excellent dispersion stability, coloring power, and light resistance.

The pigment dispersant of the present invention may be aqueous or non-aqueous. Preferably, the pigment dispersant is a dispersant in a solvent.

For example, the solvent includes: an aromatic solvent such as toluene, xylene, and methoxybenzene; an acetate solvent such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether Acetate) and propylene glycol monoethyl ether acetate; a propionate solvent, which is, for example, ethyl 3-ethoxypropionate; an alcohol solvent such as methanol and ethanol; An ether solvent, which is, for example, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol diethyl ether, and diethylene glycol dimethyl ether; a ketone solvent, which is, for example, methyl ethyl ketone or methyl meth Butanone and cyclohexanone; an aliphatic hydrocarbon solvent such as hexane; a nitrogen compound solvent such as N,N-dimethylformamide, γ-butyrolactam, N- Methyl-2-pyrrolidone, aniline, and pyridine; a lactone solvent such as γ-butyrolactone; a carbamate ester solvent such as methyl carbamate and B a 48:52 mixture of urethanes; and similar solvents.

The pigment of the present invention can be used in combination with other colorants. In this case, the other colorant may be a pigment or a dye. For example, a preferred embodiment may include a green colorant (such as for a green color filter) that is a pigment of a phthalocyanine skeleton having a blue hue and a pigment of the present invention. Formed by mixing in appropriate proportions.

Further, a surfactant or a dispersing agent may be used to further improve the dispersibility and image quality of the pigment.

<Surfactant>

Surfactants which may be used herein include various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based Surfactant.

Examples of fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781 (all from DIC Corporation (DIC Coperation) )), Fluorad FC430, 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.), and PF636, PF656, PF6320, PF6520, PF7002 (from OMNOVA Company (OMNOVA Solutions Inc.)).

The fluorine content in the fluorosurfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, and particularly from 7% by mass to 25% by mass.

Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ehter, polyoxyethylene fluorenyl Phenyl ether, ethylene oxide-oxypropylene block copolymer, t-octylphenoxyethyl polyethoxyethanol, octylphenoxyethyl polyethoxylate Oxyethanol, glycerol, trimethylol propane, trimethylolethane, and ethoxylates and propoxylates thereof (eg, glycol propoxylate, glycerol) Ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene fluorenyl Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L 31, L61, L62, 10R5, 17R2, 25R2 and Tetronic 304, 701, 704, 901, 904, 150R1, all from BASF GmbH, and Solsperse 20000 (from The Lubrizol Corporation).

Specific examples of the cationic surfactant include a tetraalkylammonium salt, an alkylamine salt, a benzalkonium salt, an alkyl pyridinium salt, and an imidazolium salt. . Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryl dimethylbenzylammonium chloride, and hexadecyl chloride Pyridine and chlorinated guanamine methylpyridine. More specific examples include a phthalocyanine derivative (EFKA-745 from Morishita & Co. Ltd.) and an organic siloxane polymer KP341 (from Shin-Etsu Chemical Co. Ltd.) (meth) acrylate (co)polymer Polyflow No. 75, No. 90, No. 95 (from Kyoeisha Chemical Co. Ltd.) and W001 (from Yusho Co. (Yusho Co.) Ltd.)).

Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium lauryl iodate, sodium alkyl diphenyl ether disulfonate, sodium alkylnaphthalene sulfonate, and Sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfonate, polyoxyethylene alkyl ether Sodium sulfate, sodium polyoxyethylene alkylphenyl ether sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, and trioctylphenoxyethoxypolyethoxyethyl sulfate Ester, the above substances can be selected as a single species or can be selected as two Species or more. Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonylphenyl ether, oxyethylene-epoxypropylene copolymerization The compound, the third octylphenoxyethylpolyethoxyethanol, and the nonylphenoxyethylpolyethoxyethanol may be selected from a single species or two or more. Specific examples include W004, W005, and W017 (from Yusho Co. Ltd.).

Examples of the fluorenone type surfactant include Toray Silicone DC3PA, SH7PA, DC11PA, 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.) BYK307, BYK323 and BYK330 (all from BYK-Chemie).

The surfactant may be used singly or in combination of two or more of the above substances.

In the case of the aqueous pigment dispersion of the present invention containing a surfactant, the content of the surfactant is not particularly limited. The above content may be, for example, 0% by mass to 100% by mass based on the mass of the pigment.

<dispersant>

Dispersants useful in the present invention include polymeric dispersants (e.g., polyamidoamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acids). Ester, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer and naphthalenesulfonic acid/ The formaldehyde condensate)) is, for example, a polyoxyethylene alkyl phosphate ester, a polyoxyethylene alkyl amine, an alkanolamine, or a pigment derivative.

The polymer dispersant can be further classified into a linear polymer, a terminally modified polymer, a graft polymer, and a block polymer according to its structure.

Examples of the terminal-modified polymer having an anchor moiety for the surface of the pigment include, for example, a terminal phosphate group as described in JP-A-H3-112992 and JP-A 2003-533455, and the like. a polymer; a polymer having a terminal sulfonic acid group as described in JP-A 2002-273191; a polymer having an organic dye partial skeleton or a hetero ring as described in JP-A-H9-77994 or the like. Further, a polymer having two or more terminal anchoring moieties (acid groups, bases, organic dye partial skeletons or heterocyclic rings, etc.) on the surface of the pigment as described in JP-A 2007-277514 has excellent dispersion stability. Sex, so it is also better.

Examples of the graft polymer having an anchoring portion to the surface of the pigment include, for example, a poly (low stretch) as described in JP-A-S54-37082, JP-A-H8-507960, JP-A 2009-258668, and the like. a reaction product of an alkylimine) with a polyester; a reaction product of a polyallylamine and a polyester described in JP-A-H9-169821; JP-A-H10-339949 and JP-A2004-37986 a copolymer of a macromonomer and a nitrogen-containing monomer; a graft polymer having an organic dye partial skeleton or a heterocyclic ring as described in JP-A 2003-238837, JP-A 2008-9426, and JP-A 2008-81732, and a macromonomer and acid containing as described in JP-A 2010-106268 a copolymer of a monomer or the like. Among them, the basic group and the acidity described in JP-A 2009-203462 are based on the dispersibility and dispersion stability of the obtained pigment dispersant and the developability shown by the curable color composition using the pigment dispersant. A group of amphoteric dispersant resins is especially preferred.

The macromonomer can be used to prepare a graft polymer having an anchoring moiety to the surface of the pigment by free radical polymerization, which comprises a conventional macromonomer, for example, by East Asia Synthesis Co., Ltd. (Toagosei) Co.Ltd.) provides macromonomer AA-6 (polymethyl methacrylate with terminal methacryl fluorenyl), AS-6 (polystyrene with terminal methacryl fluorenyl), AN-6S (copolymer of styrene and acrylonitrile having a terminal methacryl fluorenyl group) and AB-6 (polybutyl acrylate having a terminal methacryl fluorenyl group); Pula supplied by Daicel Corp. Celluloid PLACEL FM5 (addition product of 5 molar equivalents of ε-caprolactone to 2-hydroxyethyl methacrylate) and FA10L (10 molar equivalent of ε-caprolactone and 2-hydroxyethyl acrylate) An addition product); and a polyester macromonomer as described in JP-A-H2-272009. Among these macromonomers, high flexibility is preferred because of the dispersibility and dispersion stability of the obtained pigment dispersant and the developability shown by the curable color composition using the pigment dispersant. And a polyester macromonomer having a high solvent affinity, wherein the polyester macromonomer represented by the polyester macromonomer described in JP-A-H2-272009 is preferred.

Preferred block polymers having anchoring moieties for the pigment surface include The block polymer described in JP-A 2003-49110 and JP-A 2009-52010.

A commercially available product can also be used as the pigment dispersing agent of the present invention, and specific examples thereof include Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110 (by Byk-Chemie). a copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166 and 170 (high molecular weight copolymer) and BYK-P104 and P105 (high molecular weight unsaturated polycarboxylic acid); Aijia 4047, 4050 to 4010 to 4165 (polyurethane), Aijia 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (by EFKA) Polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) and 6750 (azo dye derivative); by Ajinomoto Fine Chemical Company (Ajinomoto Fine) AJISPER PB821, PB822, PB880 and PB881 supplied by -Techno Co., Inc.; FLOWLEN TG supplied by Kyoeisha Chemical Co., Ltd. -710 (urethane oligomer), POLYFLOW 50E and 300 (acrylic copolymer); by Kusumoto Chemical Co., Ltd. (Kusumoto Chemical) s,Ltd.) supplied by DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705 And DA-725; DEMOL RN, N (formalin polycondensate of naphthalenesulfonate), MS, C, SN-B (aromatic sulfonate of aromatic sulfonic acid), Hoofol provided by Kao Corporation (HOMOGENOL) L-18 (polymer polycarboxylic acid), EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) and Aseta (ACETAMIN) 86 (stearylamine acetate); SOSPERSE 5000 (phthalocyanine derivative), 2200 (azo dye derivative) supplied by Lubrizol Japan Ltd. ), 13240 (polyesteramine), 3000, 17000, 27000 (end-functionalized polymer), 24000, 28000, 32000, 38500 (graft polymer); by Nikko Chemicals, Co., Ltd.) provided by NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate); by Kawaken Fine Chemicals, Co., Ltd.) HINOACT T-8000E; Organic Oxane Polymer KP341 supplied by Shin-Etsu Chemical Co., Ltd.; Yu Yu Trading Co., Ltd. (Yusho Co., Ltd.) provides a cationic surfactant (such as W001), a nonionic surfactant (such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether) (polyoxyethylene oleyl ether), polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene Bistearate and sorbitan fatty acid esters) and anionic surfactants (such as W004, W005 or W017); Aijia-46, Aijia from Morishita & Co., Ltd. 47. Aijia-47EA, EFKA POLYMER 100, Aijia Polymer 400, Aijia Polymer 401 and Aijia Polymer 450; a polymeric dispersant supplied by San Nopco Limited (eg DISPERSE AID 6, DSM 8, DS 3 and DS8; ADEKA PLURONIC L31, supplied by ADEKACorp. F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 and P-123; and Inet (provided by Sanyo Chemical Industries, Ltd.) IONET) S-20.

These pigment dispersants may be used singly or in combination of two or more. In particular, in the present invention, the pigment derivative and the polymer dispersant are preferably used in combination. Further, the pigment dispersant of the present invention may be used by combining a terminal-modified polymer, a graft polymer or a block copolymer having an anchor moiety with respect to the surface of the dye with an alkali-soluble resin. The alkali-soluble resin includes a (meth)acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and The side chain has an acid cellulose derivative of a carboxylic acid and a resin obtained by a hydroxyl group-containing polymer modified with an acid anhydride, and among them, a (meth)acrylic copolymer is particularly preferable. N-substituted maleimide monomer substituted at the N position described in JP-A-H10-300922, ether dimer copolymer described in JP-A 2004-300204, and JP- The alkali-soluble resin containing a polymerizable group described in A-H7-319161 is also preferable.

In the case of an aqueous dispersant, the dispersing agent described in paragraphs [0487] to [0516] of JP-A 2012-158736 can be used.

In the composition of the present invention, the dispersing amount is preferably from 1 to 80 parts by mass, more preferably from 5 to 70 parts by mass, even more preferably from 10 to 100 parts by mass per 100 parts by mass of the pigment used as the coloring material. 60 parts by mass.

Specifically, for every 100 parts by mass of the pigment, the polymer dispersant The amount is preferably in the range of 5 to 100 parts by mass, more preferably in the range of 10 to 80 parts by mass.

When a pigment derivative is also used, the amount of the pigment derivative is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 3 to 20 parts by mass, particularly preferably per 100 parts by mass of the pigment. It is in the range of 5 to 15 parts by mass.

The dispersant content for preparing the pigment dispersant of the present invention is preferably from 1% by mass to 90% by mass, more preferably from 3% by mass to 70% by mass based on the total solids of the pigment in the pigment dispersant.

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

In the present invention, the volume average particle size of the pigment is preferably 10 nm or more and 250 nm or less. As used herein, the term "volume average particle size" of a pigment particle refers to the particle size of the pigment itself, or if the additive is deposited on the pigment, the "volume average particle size" refers to a pigment plus an additive such as a dispersant. Particle size. In the present invention, the volume average particle size was measured using a Nanotrack UPA particle size analyzer (UPA-EX150, available from Nikkiso Co. Ltd.). A measuring cell containing 3 ml of each pigment dispersing agent was used and measured according to a specific procedure. The parameters input during the measurement include the viscosity of the ink for stickiness and the color used for the density of the dispersed particles. Prime density.

More preferably, the volume average particle size is 20 nm or more and 250 nm or less, and still more preferably 30 nm or more and 230 nm or less. If the number of particles in the pigment dispersant has an average particle size of less than 20 nm, the storage stability of the pigment dispersant may not be ensured, however, if the particle size exceeds 250 nm, the optical density may be reduced.

Preferably, the pigment concentration in the pigment dispersant of the present invention is from 0.1% by weight to 50% by weight, more preferably from 3% by weight to 45% by weight, particularly preferably from 7% by weight to 40% by weight, based on the total solids. .

The pigment of the present invention is used by adjusting the characteristics (for example, solvent resistance, dispersibility, and thermal conductivity) of the dye of the present invention by using a substituent to suit the application target. Further, depending on the system used, the pigment of the present invention can be used in an emulsified/dispersed state or a solid-dispersed state.

(color composition)

The colored composition of the present invention is characterized in that it comprises at least one of the above-mentioned pigments. Preferably, the colored composition of the present invention is a radiation sensitive color composition.

The color composition or the radiation-sensitive color composition of the present invention can be conveniently used as a color resist liquid, an ink for inkjet printing, and a color composition for a color filter. The colored composition of the present invention can be prepared by dispersing the pigment of the present invention in a vehicle. The color composition of the present invention includes a composition that is used as an ink and has no medium. The color composition of the present invention may contain other additives as long as it does not affect the effects of the present invention. Other additions include conventional additions (described in JP-A 2003-306623), which is, for example, an anti-drying agent (humectant), an anti-fading agent, an emulsion stabilizer, a permeation accelerator, and an ultraviolet UV absorber, preservative, anti-mold agent, pH modifier, surface tension modifier, antifoaming agent, viscosity modifier, dispersant, dispersion stabilizer , rust inhibitors, chelating agents, etc. In the case where the ink is water-soluble, these various additives can be directly added to the ink liquid. In the case where the ink is oil-soluble, these various additives are usually added to the pigment dispersant after the preparation of the pigment dispersant, but various additives may be added to the oil phase or the aqueous phase during preparation.

Further, the composition of the present invention may include other pigments and/or dyes within the scope not departing from the object of the present invention. The amount of the above dye and/or dye is preferably 1% by weight or less compared to all the colorants contained in the composition. For example, the following pigment materials can be used: JP-A-S64-90403, JP-A-S64-91102, JP-A-H01-94301, JP-A-H06-11614, JP registration number 2592207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,676,920, U.S. Patent No. 505,950, U.S. Patent No. 5,676,920, JP-A-H05-333,207, JP-A-H06-35,183, JP-A-H06-51115, JP- A-H06-194828. The structure of the above pigment is, for example, pyrazoleazo, anilinozo, triphenylmethane, anthracene, benzylidene, oxonol, pyrazolo triazoleazo. ), pyridoneazo, cyanine, phenothiazine, pyrrolopyrazole azo. The above-mentioned colorant multimer composite can be cited as JP-A-2011-213925 or JP-A-2013-041097 The disclosed compounds.

[inkjet ink]

The inkjet ink of the present invention (hereinafter sometimes referred to as "ink") uses a pigment dispersant, and it is preferred to prepare the inkjet ink of the present invention by mixing a water-soluble solvent, water, or the like. The pigment dispersant of the present invention can be used by itself if there is no particular problem.

The content of the pigment dispersant in the ink of the present invention is preferably in the range of 1% by mass to 100% by mass, taking into consideration the hue, color density, chroma and transparency of the image formed on the recording medium. More preferably, it is in the range of 3 mass% to 20 mass%, and particularly in the range of 3 mass% to 10 mass%.

The content of the pigment of the present invention is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.2 part by mass or more and 10 parts by mass or more per 100 parts by mass of the ink of the present invention. It is less, and more preferably from 1 part by mass to 10 parts by mass. Other pigments can be used in the ink of the present invention together with the pigment of the present invention. When two or more kinds of pigments are used in combination, the total content of the pigment preferably falls within the above range.

The ink of the present invention can be used not only for the formation of a monochrome image but also for the formation of a full-color image. Magenta ink, cyan ink, and yellow ink can be used to form a full-color image, and black ink can be additionally used for color adjustment.

In the ink of the present invention, the above pigment can be used together with other pigments. Examples of yellow pigments that can be used 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 pigments which may be used include C.I.P.V.19 and C.I.P.R.122, and cyan pigments which may be used include C.I.P.B.15:3 and C.I.P.B.15:4. In addition to the above pigments, any coloring matter can be used for each color. Examples of black materials that can be used include disazo, trisazo, and tetrazolium pigments, as well as carbon black dispersants.

The water-soluble solvent which can be used for the inkjet ink of the present invention includes polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, and sulfur-containing solvents.

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

Examples of the polyol derivative include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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 diethylene glycol adducts.

Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine, and examples of the alcohol include ethanol, isopropanol, butanol, and benzyl alcohol, and sulfur Examples of the solvent include thiodiethanol, thiodiglycerol, sulfolane, and dimethylsulfoxide. In addition to the above, propyl carbonate, ethyl carbonate, and the like can also be used.

The water-soluble solvent used in the present invention may be used singly or in combination of two or more. The content of the water-soluble solvent is 1% by mass or more of the total ink and 60% by mass or less, 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 degree of optical density may not be obtained in some cases, and when the above content exceeds 60% by mass, the ink liquid may be more viscous and exhibits in an ink jet performance. It may be unstable.

Preferred features of the inkjet ink of the present invention are as follows.

The surface tension of the ink is preferably 20 mN/m or more and 60 mN/m or less, more preferably 20 mN/m or more and 45 mN/m or less, and still more preferably 25 mN/m or more. 35mN/m or less. If the surface tension is less than 20 mN/m, liquid may spill on the surface of the nozzle of the recording head, and normal printing may be suppressed. On the other hand, if the above surface tension exceeds 60 mN/m, the ink may be difficult to penetrate into the recording medium after printing, and the drying time may be increased.

The surface tension was similarly measured as described above using a Wilhelmy surface tension meter at 23 ° C, 55% RH.

The viscosity of the ink is preferably 1.2 mPa. s or greater and 8.0mPa. s or smaller, more preferably 1.5mPa. s or greater and 6.0mPa. s or smaller, and preferably 1.8 mPa. s or larger and 4.5mPa. s or smaller. If the above viscosity is more than 8.0mPa. s, the ink ejection efficiency may be degraded. On the other hand, if the above viscosity is less than 1.2mPa. s, the ink may deteriorate in long-term ink jet performance.

At a shear rate of 1400s ^-1 and 23 ℃ using a rotary viscometer (rotational viscometer) Rheomat 115 (from Contraves Advanced Devices (Contraves Advanced Devices Sdn.Bhd.)) Measured viscosity (including those described in the follow-up).

In addition to the above components, water can be added to the ink in a range in which the surface tension and the viscosity can be adjusted to the above preferred ranges. Although the amount of addition of water is not particularly limited, it is preferably 10% by mass or more and 99% by mass or less, and more preferably 30% by mass or more and 80% by mass or less, based on the total mass of the ink.

For further needs such as feature control to improve jetting performance, inks can be used with polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, cellulose derivatives (eg It is ethyl cellulose and carboxymethyl cellulose), polysaccharides and derivatives thereof, water-soluble polymers, polymeric emulsions (for example, acrylic acid emulsions), polyurethane-based emulsions, and hydrophilicity. Latex, hydrophilic polymeric glue, cyclodextrin, large cyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamidine, anthraquinone Ketone surfactants and fluorosurfactants.

Further, in order to adjust the conductivity and pH, it is possible to use an alkali metal compound (which is, for example, potassium hydroxide, sodium hydroxide, and lithium hydroxide), a nitrogen-containing compound (for example, ammonium hydroxide, triethanolamine, diethanolamine). , ethanolamine and 2-amino-2-methyl-1-propanol), alkaline earth metal compounds (such as calcium hydroxide); acids (such as sulfuric acid, hydrochloric acid and nitric acid) and strong acids and weak bases Salt (which is for example ammonium sulphate).

Examples of other selectively added additives include pH buffers, antioxidants, anti-mold agents, viscosity modifiers, conducting agents, and ultraviolet absorbers.

[Color resist]

The curable color composition of the present invention is characterized in that it comprises at least one of the above-mentioned pigments. Preferably, the curable color composition is a radiation-sensitive color composition that is cured by radiation.

Preferably, the radiation sensitive color composition of the present invention further comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a solvent.

During the preparation of the radiation sensitive color composition of the present invention, the above-mentioned dye may be directly added, or a pigment dispersed in a solvent may be added. Since excellent color characteristics, durability, dispersant stability, light resistance, and weatherability can be attained, the coloring matter is preferably added in the form of a pigment dispersing agent.

The amount of the dye in the radiation sensitive composition of the present invention (the total amount of the dye if any other pigment is used in combination) is preferably 0.01 to 2 parts by mass, and more preferably 0.1, based on 1 part by mass of the polymerizable compound. Up to 1 part by mass.

<alkali soluble resin>

The radiation sensitive color composition of the present invention more preferably contains an alkali soluble resin. By including an alkali-soluble resin, the composition can improve developability and pattern formability.

The alkali-soluble resin may be arbitrarily selected from those in the form of a linear organic polymer, and in the molecule of the alkali-soluble resin (more preferably, having an acrylic copolymer or a styrene-type copolymer as a main chain) The molecule has at least one group capable of increasing alkali solubility.

In the process of preparing an alkali-soluble resin by radical polymerization, any publicly known method based on radical polymerization can be used. The technical field has a pass A person skilled in the art can easily set conditions of a polymerization reaction in the process of preparing an alkali-soluble resin by radical polymerization, such as temperature, pressure, kind and content of a radical initiator, types of solvents, and the like, and The above conditions can also be determined experimentally.

The linear organic high molecular polymer used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in its side chain, and examples of the polymer include a methacrylic acid copolymer, an acrylic copolymer, and itaconic acid copolymerization. , crotonic acod copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, alkali soluble phenolic resin (for example, novolac resin), having a carboxylic acid in its side chain An acidic cellulose derivative and an adduct of a polymer having a hydroxyl group and an acid anhydride. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable with (meth)acrylic acid is preferred as the alkali-soluble resin. Other monomers copolymerizable with (meth)acrylic acid are, for example, alkyl (meth)acrylate, aryl (meth)acrylate, and vinyl compounds. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, Methyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and vinyl compounds such as styrene, α-methyl styrene, vinyl toluene, (meth)acrylic acid Glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl (meth) acrylate, macromonomer of polystyrene, giant monomethyl methacrylate The N-substituted maleimide monomer (for example, N-phenylmaleimide and N-cyclohexenyl maleimide) described in JP-A-H10-300922. These other monomers copolymerizable with (meth)acrylic acid may be used singly or in combination of two or more.

As the alkali-soluble resin, it is also preferred to use the polymer (a) which is configured by polymerizing a monomer component which substantially comprises the following compound represented by the formula (ED) (hereinafter also It is called "ether dimer".

(In the formula (ED), R ¹ and R ² each independently represent a C _1-25 hydrocarbon group which may have a hydrogen atom or a substituent.) The alkali-soluble resin preferably further contains the polymer (a) as an essential polymer component (A) The polymer (a) is configured by polymerizing a monomer component substantially comprising a compound represented by the formula (ED). With the above configuration, the curable resin composition of the present invention can form a cured coating film which is excellent in heat resistance and transparency. In the formula (ED) representing an ether dimer, the C _1-25 hydroxyl group represented by R ¹ and R ² (which may have a substituent) is not particularly limited, and C ₁ represented by R ¹ and R ² Examples of the _-25 hydroxy group include a straight chain-like or a branched alkyl group, which is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or Tributyl, third amyl, stearyl, lauryl and 2-ethylhexyl; aryl, which is, for example, phenyl; alicyclic, which is, for example, cyclohexyl, tert-butylcyclohexyl, Dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl and 2-methyl 2-adamantyl; alkyl substituted by alkoxy, for example 1- A methoxyethyl group and a 1-ethoxyethyl group; and an alkyl group substituted with an aryl group, which is, for example, a benzyl group. Among these groups, a substituent having a primary carbon or a secondary carbon is particularly preferable from the viewpoint of heat resistance, and is, for example, a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group. The mass is less susceptible to being removed by acid or heat.

Specific examples of the ether dimer which can be used in the present invention are as described in paragraphs [0242] to [0244] of JP-A-2012-063735.

As the alkali-soluble phenol resin, the curable color composition of the present invention is preferably used when it is configured as a composition of a positive composition. The alkali-soluble phenol resin is, for example, a novolak resin and a vinyl polymer.

The novolak resin is obtained, for example, by condensing phenols and aldehydes in the presence of an acidic catalyst. The phenols are, for example, phenol, cresol, acetol, butanol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, Naphthol and bisphenol A.

The aldehydes are, for example, formaldehyde, paraformaldehyde, acetoaldehyde, propionaldehyde, and benzaldehyde.

The phenols and aldehydes may be used singly or in combination of two or more.

Specific examples of the novolak resin include metacresol, paracresol or a mixture thereof and a condensate of formalin.

The molecular weight distribution of the novolac resin can usually be adjusted by fractionation. A novolak resin and a low molecular weight component having a phenolic hydroxyl group (for example, bisphenol C or bisphenol) A) Mixing.

The alkali-soluble phenol resin may include a structural unit derived from an ethylenic unsaturated monomer, and the above ethylenically unsaturated monomer is represented by the formula (X).

Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (which may include a benzene ring) , n is an integer from 1 to 15.

In the above formula (X), the alkyl group of R ² preferably has 2 to 3 carbon atoms. The alkyl group of R ^{3 has} a carbon number of 1 to 20, preferably 1 to 10, and the alkyl group of R ³ may include a benzene ring. The alkyl group represented by R ³ which includes a benzene ring is, for example, a benzyl group and a 2-phenyl (iso)propyl group.

In order to improve the crosslinking efficiency of the curable color composition of the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the alkali-soluble resin having a polymerizable group which can be used include a propylene group, a (meth) acrylonitrile group, an allyloxyalkyl group, and the like in a side chain thereof. Examples of the polymer having a polymerizable group include the Dianal NR series (from Mitsubishi Rayon Co. Ltd.), Photomer 6173 (COOH-containing polyurethane oligomer), From Diamond Shamrock Co. Ltd., Viscoat R-264, KS Resist 106 (from Osaka Organic Chemical Industry) Ltd.)), Cyclomer P series, Placcel CF200 series (both from Daicel Chemical Industries, Ltd.), and Ebecryl 3800 (from Daicel-UCB). Preferred examples of the alkali-soluble resin having a polymerizable group include a urethane-modified polymerizable double bond-containing acrylic resin which is left by a preliminary reaction between an isocyanate group and an OH group. The isocyanate group is unreacted and obtained by a (meth)acryl-containing fluorenyl compound and a carboxyl group-containing acrylic resin; an unsaturated group-containing acrylic resin which has a carboxyl group-containing acrylic resin and has a molecule thereof A compound obtained by reacting an epoxy group and a polymerizable double bond; an acid-pendant epoxy acrylic resin; an acrylic resin containing a polymerizable double bond, which is obtained by an OH-containing acrylic resin a dibasic anhydride reaction of a polymerizable double bond; a resin obtained by reacting an OH-containing acrylic resin, isocyanic acid, and a polymerizable group-containing compound; and by having an ester group on the side thereof A resin obtained by subjecting a resin of a chain to alkali treatment, wherein the ester group has a leaving group such as a halogen atom or a sulfonate group at the α-position or the β-position (for example, JP-A-2002-229207 and JP-A) - described in 2003-335814).

Particularly preferred examples of the alkali-soluble resin include a benzyl (meth)acrylate/(meth)acrylic copolymer and a multicomponent copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Things. Other examples include copolymers containing the following described in JP-A-H07-140654: 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate/polystyrene macromonomer/methacrylic acid benzoate Ester/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy methacrylate Ethyl / poly Styrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer.

The acid value of the alkali-soluble resin is preferably from 30 mg KOH/g to 200 mg KOH/g, more preferably from 50 mg KOH/g to 150 mg KOH/g, and most preferably from 70 to 120 mg KOH/g. The weight average molecular weight (MW) of the alkali-soluble resin is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000, and most preferably from 7,000 to 20,000.

As not specifically described, the weight average molecular weight is measured by Gel Permeation Chromatography (GPC). GPC was measured by removing the solvent from the obtained polymer to separate the solid, and diluting the obtained solid with tetrahydrofuran to a concentration of 0.1% by mass, followed by using HLC-8020GPC manufactured by Tosoh Corporation and manufactured by Tosoh Corporation. The TSKgel Super Multipore HZ-H three-column column is connected in series to form a column (4.6 mm ID and 15 cm long). Measurement conditions: a sample concentration of 0.35% by weight, a flow rate of 0.35 ml/min, an injection amount of 10 μl, a measurement temperature of 40 ° C, and an RI detector were used.

The content of the alkali-soluble resin in the curable color composition is preferably from 1% by mass to 15% by mass, more preferably from 2% by mass to 12% by mass, and particularly from 3% by mass to 10% by mass based on the total solid content of the composition. quality%.

<Polymerizable compound>

The polymerizable compound is arbitrarily selectable in consideration of the manufacturing process of the color filter. The polymerizable compound is, for example, a photosensitive compound and/or a thermosetting compound, and among them, a photosensitive compound is particularly preferable.

More specifically, the polymerizable compound is selected from the group consisting of compounds having at least one (and preferably two or more) terminal ethylenic unsaturated bonds. Such compounds are well known in the related art, and such compounds can also be used in the present invention without particular limitation. The above compounds may be in any chemical form including monomers, prepolymers (i.e., dimers, trimers, and oligomers), or mixtures thereof, and their multimers. The polymerizable compounds of the invention may be used singly or in combination of two or more.

More specifically, examples of monomers and related prepolymers include: unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid), esters thereof, and Its amides, as well as its polymers. Among these examples, preferred are esters formed from unsaturated carboxylic acid and aliphatic polyol compounds, and decylamines formed from unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Classes, and their polymers. Other preferred examples include addition products which are unsaturated carboxylic acid esters or guanamines having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group, and a monofunctional or polyfunctional isocyanate. Or an epoxy compound; and a dehydration condensation product formed from an unsaturated carboxylic acid ester or a guanamine and a monofunctional or polyfunctional carboxylic acid. Still more preferred examples include: addition products, carboxylic acid esters or guanamines having an electrophilic substituent (for example, an isocyanate group or an epoxy group) and a monofunctional or polyfunctional alcohol. , an amine or a thiol; and a substituted product which is unsaturated by having a detached substituent such as a halogen-containing group or a tosyloxy group And carboxylic acid esters or guanamines and monofunctional or polyfunctional alcohols, amines or thiols. In addition to the above, it is also possible to use the following to replace the above unsaturated carboxylic acid: an unsaturated phosphonic acid, a vinylbenzene derivative (for example, styrene, vinyl ether, and propylene ether). .

As specific examples of these compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 are also preferably used in the present invention.

The above polymerized compound is also preferably a compound having an ethylenically unsaturated group and having a boiling point of 100 ° C or higher under normal pressure, which is composed of a polymerizable monomer each having at least one addition polymerization. (addition-polymerizable) of the ethyl group. Specific examples include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (methyl) Acrylate; a polyfunctional acrylate or methacrylate such as polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di( Methyl) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate Ester, dipentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether, and tris(propylene oxy oxyethyl) isocyanate An addition product of a polyhydric alcohol, such as glycerol esterified with (meth) acrylate or trimethylolethane having a pendant ethyl oxide or a propyl oxide; JP-B-S48-41708 , urethane (meth) acrylate (urethane) described in JP-B-S50-6034 and JP-A-S51-37193 (meth)acrylate); polyacrylates described in JP-A-S48-64183, JP-B-S49-43191, and JP-B-S52-30490; polyfunctional acrylates and methacrylates, For example, an epoxy acrylate obtained by a reaction product of an epoxy resin and (meth)acrylic acid; and a mixture of the above.

Commercially available products of these polymeric compounds include: urethane oligomers UAS-10, UAB-140 (from Sanyo Kokusaku Pulp Co. Ltd.), UA-7200 (from Shin) -Nakamura Chemical Co. Ltd.), DPHA-40H (from Nippon 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 by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group (for example, glycidyl (meth) acrylate) Polyfunctional (meth) acrylate.

Other preferred examples of the polymerizable compound include a compound having an anthracene ring and two or more ethylenic polymerizable groups, which are, for example, JP-A-2010-160418, JP-A-2010-129825, Japanese Patent 4364216 Described in the article, as well as cardo resin.

Preferable examples of the compound having a boiling point of 100 ° C or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group include paragraphs [0254] to [0257] of JP-A-2008-292970 The compounds described in the above.

In addition to the above substances, it is also preferred to use the JP-A-2011-180307 The radical polymerizable monomer described in the paragraph [0193], and the formula (MO-1) to the formula in paragraphs [0093] to [0094] of JP-A-2012-046712 (MO-5) is indicated.

A compound represented by the formula (1) and the formula (2) in JP-A-H10-62986 (a specific example is shown in JP-A-H10-62986) can be used as the polymerizable compound, which can be stretched by Ethyl oxide or propyl oxide is added to the polyol and then obtained by esterification with (meth)acrylic acid.

Among them, preferred examples of the polymerizable compound include dipentaerythritol triacrylate (commercially available, such as KAYARAD D-330, from Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available, such as KAYARAD) D-320 from Nippon Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available, such as KAYARAD D-310 from Nippon Kagaku), dipentaerythritol hexa(meth) acrylate (commercial It is available, such as KAYARAD DPHA, from Nippon Kayaku Co., Ltd., and has a chain of (meth)acrylonyl and ethylene glycol or propylene glycol residues in the structure. Oligomers of these polymerizable compounds can also be used.

The polymerizable compound may also be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonate group, a phosphate group or the like. Therefore, if the compound is used in the form of the above mixture (in which the unsaturated carboxyl group is retained), the ethylenic compound can be used as it is. Alternatively, if desired, the ethylenic compound can be introduced into the acid group by reacting its hydroxyl group with a non-aromatic carboxylic anhydride. Specific examples of non-aromatic carboxylic anhydrides usable herein include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid group is an ester formed of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which is preferably reacted by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. The resulting polyfunctional monomer incorporating an acid group, and particularly wherein the aliphatic polyhydroxy compound is an ester of pentaerythritol and/or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers from the East Asian Synthetic Company.

Although each of these monomers can be used alone as itself, since it is very difficult to use a single compound in the manufacturing process, it is also possible to use two or more of these monomers in a mixed manner. If necessary, it is also possible to use a combination of an acid group-free polyfunctional monomer and an acid group-containing polyfunctional monomer as the above monomer.

The acid value of the acid group-containing polyfunctional monomer is preferably from 0.1 to 40 mg KOH/g, and particularly from 5 to 30 mg KOH/g. If the acid value of the polyfunctional monomer is too small, the solubility characteristics in the development manufacturing method may be deteriorated, but too large an acid value may deteriorate the easiness in manufacturing and handling, and may cause photopolymerization (photo-polymerization). The ability to deteriorate, as well as the curing performance that may be sufficient to ensure surface smoothness on the pixels. Therefore, when two or more polyfunctional monomers having different acid groups are used, or when a polyfunctional monomer having no acid group is used in combination, the acid value of the entire polyfunctional monomer is adjusted to Necessary in the above range of.

The polymerizable compound preferably comprises a polyfunctional monomer having a carpolactone structure as a polymerizable monomer, and a polyfunctional monomer having a caprolactone structure usable herein includes JP-A-2012- Described in paragraphs [0155] through [0162] of 003225.

The polymerizable compound also preferably comprises a monomer selected from the group consisting of compounds represented by formula (i) or (ii) described in paragraphs [0029] to [0040] of JP-A-2010-085457 ( As a polymerizable monomer).

The acid group-containing ethylenically unsaturated compound is also suitable for use in the polymerizable compound. The acid group-containing ethylenically unsaturated compound is usually obtained by converting a part of the hydroxyl group of the polyol into a (meth) acrylate and converting them into a carboxyl group by adding an acid anhydride to the residual hydroxyl group. Commercially available products include M-510 and M-520, which are polyacid-modified acrylic oligomers from East Asia Synthesis.

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

The polymerizable compound also preferably includes a polymerizable compound containing an alkoxy group. The alkylene group-containing polymerizable compound which can be used includes the polymerizable compound described in paragraphs [0031] to [0047] of JP-A 2009-175724.

The content of the polymerizable compound is from 20% by mass to 90% by mass, and preferably from 40% by mass to 80% by mass.

The content of the polymerizable compound is preferably from 40% by mass to 95% by mass, and more preferably from 50% by mass to 90% by mass based on the total solid content of the color filter. If necessary, other resins may be added to the above composition, and the total content including other resins preferably falls within the above range. It should be noted that the total solid content refers to the amount of the component which exists in a solid form after drying and solidification of the above composition, which does not contain a solvent but contains a monomer.

<Polymerization initiator>

The radiation sensitive color composition of the present invention preferably comprises a polymerization initiator. The polymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and the polymerization initiator can be arbitrarily selected from known photopolymerization initiators. Preferred examples include those having photosensitivity from the ultraviolet radiation region to the visible region, which is, for example, an activator that interacts with the photoexcited sensitizer in some manner to produce activated radicals, and The initiator of the initial cationic polymerization is determined by the type of monomer.

The photopolymerization initiator preferably comprises at least one of the following components: a molecular absorption coefficient of about 50 in a wavelength range of from about 300 to 800 nm, more preferably from 330 to 500 nm.

Examples of the photopolymerization initiator include: a halogenated hydrocarbon derivative (for example, a one having a triazine skeleton, having an oxadiazole skeleton), an acylphosphine compound such as a ruthenium phosphine oxide. An oxime compound, which is, for example, a hexaarylbiimidazole and an anthracene derivative; an organic peroxide; a sulfur-based compound; a ketone compound; an aromatic onium salt; a ketoxime; an aminoacetophenone compound (aminoacetophenone); and oxyacetophenone.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include compounds described in W. Bayakashi et al., Bull. Chem. Soc. Japan, No. 42, 2924 (1969), in the British Patent No. A compound described in No. 1388492, a compound described in JP-A-S53-133428, a compound described in German Patent No. 3337024, and an organic chemical journal by J. Org. Chem., No. 29 , a compound described in 1527 (1964), a compound described in JP-A-S62-58241, a compound described in JP-A-H05-281728, a compound described in JP-A-H05-34920, and a US patent. The compound described in No. 4212976.

In addition to the above, examples of the photopolymerization initiator which can be used herein include the polymerization initiator described in paragraph [0016] of JP-A-2012-053243.

The ketone compound which can be used herein includes those described in paragraph [0117] of JP-A-2012-053243.

It is also preferred to use a hydroxyacetophenone compound, an aminoacetophenone compound, and a phosphonium phosphine compound as photoinitiator. More specifically, an aminoacetophenone type initiator as described in JP-A-H10-291969 and a phosphonium oxide type initiator as described in Japanese Patent No. 4225899 can be used.

Examples of the aminoacetophenone type initiators usable herein include Irgacure-184, Darocur-1173, Irgacure-500, Irgacure-2959, and Irgacure-127 (trade names, all from Bakif). Examples of the aminoacetophenone type compound include commercially available Irgagure-907, Irgacure-369, and Irgacure-379 (trade name, all from Bakif). The compound described in JP-A-2009-191179 (which absorbs a long wavelength source having a wavelength of 365 nm or 405 nm) is also used as the aminoacetophenone type compound. Examples of the phosphonium-type initiators usable herein include commercially available Irgagure-819 and Darocur-TPO (trade names, both from Bakif).

The photopolymerization initiator is more preferably, for example, a quinoid compound. Specific examples of the oxime-type 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.

Examples of the ruthenium compound are, for example, an anthracene derivative (used preferably as a photopolymerization initiator in the present invention), and the anthracene derivative includes: 3-benzylideneoxyiminobutan-2-one (3- Benzoyloxyiminobutane-2-one), 3-acetoxyiminobutan-2-one, 3-propoxyanilidebutan-2-one, 2-ethyloxyiminopentane 3-keto, 2-ethoxymethoxyimino-1-phenylpropan-1-one, 2-benzylideneoxyimino-1-phenylpropan-1-one, 3-(4 -Toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of the oxime ester compound include the compounds described in the following publications: pages 1653 to 1660 of JCS Perkin II (1979); pages 156 to 162 of JCS Perkin II (1979); Journal of Photopolymer Science and Technology ( Journal of Photopolymer Science and Technology; 1995), pp. 202-232; JP-A-2000-66385, JP-A-2000-80068, PCT International for Patent Application (JP, A) No. 2004-534797 a public Japanese translation of the publication and JP-A-2006-342166. Commercially available products preferably used herein include Irgagure-OXE01 and Irgagure-OXE02 (both from BASF). Further, for example, the following commercial products: TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS) can also be used.

In addition to the above, examples of the oxime ester compound which can be used herein include, as described in the PCT International Publication No. 2009-519904, the disclosure of the patent application (JP, A) No. 2009-519904 a compound having a nitrogen atom of a ring; a compound having a hetero-substituent in the benzophenone moiety as described in U.S. Patent No. 7,626,957; for example, JP-A-2010-15025 and U.S. Patent No. 2009/292039 a compound having a nitro group introduced in a dye moiety as described in the No.; a ketone oxime type compound described in International Patent Publication No. 2009-131189; a triazine having a molecule in one molecule as described in US Pat. No. 7556910 a compound of a skeleton and an anthracene skeleton; and a compound which exhibits maximum absorption at 436 nm and thus is highly sensitive to a g-line source as described in JP-A-2009-221114.

It is also suitable to use the cyclic oxime compound described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, from the viewpoint of sensitizing, it is particularly preferred to link the carbazole dye to form a condensed ring therewith (described in JP-A-2010-32985 and JP-A-2010). -185072) This is due to their high absorbance.

It is also suitable to use an unsaturated bond at a specific position of the ruthenium compound. The compounds (described in JP-A-2009-242469) are due to their ability to regenerate active free radicals from polymerization-inactive free radicals.

Particularly preferred examples include an anthracene compound having a specific substituent as described in JP-A-2007-269779, and an anthracene compound having a sulfur aryl group as described in JP-A-2009-191061. More specifically, a ruthenium type photopolymerization initiator described in JP-A-2012-032556 is preferably used.

Two or more kinds of radical photopolymerization initiators usable in the present invention may be used in combination as needed. The content of the radical photopolymerization initiator in the radiation sensitive composition (or total content if two or more substances are contained) is preferably 0.1% by mass of the total solid content of the radiation sensitive composition to In the range of 20% by mass, more preferably in the range of 0.5% by mass to 10% by mass, and particularly in the range of 1% by mass to 8% by mass. In these ranges, a good degree of sensitivity and pattern formation can be obtained.

In order to improve the radical generating efficiency and to move the photosensitive wavelength toward the longer end, a sensitizer may be included in the present invention. The sensitizer which can be used in the present invention is preferably any one which can sensitize the radical photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

The sensitizer which can be used in the present invention is, for example, the compound described in paragraphs [0101] to [0154] of JP-A-2008-32803.

From the viewpoint of light absorption efficiency in the deep portion and the efficiency of degradation at the beginning, the content of the sensitizer based on the solid content It is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.5% by mass to 15% by mass.

The sensitizer may be used alone, or two or more sensitizers may be combined.

<Other ingredients>

[Organic solvents]

The radiation sensitive color composition of the present invention may comprise at least one organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of the co-existing component and the coatability of the curable color composition produced, and particularly dissolves the binder. The organic solvent is preferably selected in consideration of properties, coatability and safety.

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, and butyl Ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (especially methyl methoxyacetate, methoxyacetate B) Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate), alkyl 3-oxopropionate (eg methyl 3-oxopropionate, and ethyl 3-oxopropionate (especially Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate), alkyl 2-oxopropionate (eg 2-oxo) Methyl propionate, ethyl 2-oxopropionate and propyl 2-oxopropionate (especially methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate (especially Methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate), Acetone A Ester, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetate, methyl 2-oxobutanate and ethyl 2-oxobutyrate.

For example, the ethers are described, for example, in JP-A-2012-046712. The ketones are, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone. The aromatic hydrocarbons are preferably, for example, toluene and xylene.

From the viewpoints of the solubility of the above-mentioned individual components, the solubility of the alkali-soluble polymer (if contained), and the improvement of the surface to be coated, two or more kinds of these organic solvents may be mixed, and JP-A- may be referred to. The composition described in 2012-046712.

The 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 15% by mass to 60% by mass.

[crosslinking agent]

A crosslinking agent may be additionally added to the curable color composition used in the color filter of the present invention in order to increase the hardness of the color cured film obtained by curing the curable color composition.

The crosslinking agent is not particularly limited as long as it can cure the film by a crosslinking reaction, and the crosslinking agent is, for example, (a) an epoxy resin; (b) is selected from a methylol group, a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent of an alkoxymethyl group and a decyloxymethyl group; and (c) selected Phenol substituted with at least one substituent from hydroxymethyl, alkoxymethyl and decyloxymethyl a compound, a naphthol compound or a hydroxy hydrazine compound. Among these crosslinking agents, a polyfunctional epoxy resin is preferred.

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

The colored composition of the present invention may comprise a surfactant.

The weight average molecular weight (Mw) of the copolymer used as the surfactant is preferably 1,500 or more and 5,000 or less.

The surfactant may be used singly or two or more kinds of surfactants may be combined.

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

The colored composition of the present invention may comprise a dispersing agent. The content of the dispersant is preferably 60 parts by weight or less, more preferably 5 parts by weight to 45 parts by weight, and still more preferably 10 parts by weight to 40 parts by weight per 100 parts by weight of the specific resin.

[Polymerization inhibitor]

The curable color composition of the present invention should desirably contain a small amount of a polymerization inhibitor to inhibit unwanted thermal polymerization of the polymerizable compound during or during storage of the curable color composition.

Polymerization inhibitors which can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, tert-butyl T-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butyl Phenol), 2,2'-extended methyl bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerous salt and the like.

The polymerization inhibitor is preferably added in an amount of from about 0.01% by mass to about 5% by mass based on the total mass of the composition.

<Preparation of Radiation-Linear Color Composition>

The preparation method of the radiation sensitive color composition of the present invention is not particularly limited, and may be, for example, a mixed coloring matter, a polymerizable compound, and a photopolymerization initiator which is selectively added, and various additives, and further mixed with the remaining The amount of solvent.

In the preparation of the curable color composition for the color filter of the present invention, in order to remove foreign matter and reduce defects, it is preferred to filter a mixture of a plurality of components via a filter. The filter used herein may be arbitrarily selected from those already used for the filter, and is not particularly limited. Specific examples include those composed of a fluorine-containing resin such as polytetrafluoroethylene (PTFE); polyamine type resins such as nylon-6 and nylon-6,6; and polyolefin resins. For example, polyethylene and polypropylene (PP) (including high density type and ultra-high molecular type). Among these filter materials, for example, polyamide-6 and nylon-6,6 polyamine type resins and polypropylene (including high density polypropylene) are preferable.

The pore diameter of the filter is suitably from about 0.01 μm to about 7.0 μm, preferably from about 0.01 μm to about 2.5 μm, and more preferably from about 0.01 μm to about 2.0 μm. In these ranges, fine-grained foreign matter can be removed in a large amount (which may inhibit the preparation of a uniform curable color composition in a subsequent manufacturing method) in order to ensure uniform and smooth formation. Curing the colored composition.

The filter used herein can be a combination of different types of filters. In this case, the first filter filtration may be performed one or two times or more. Alternatively, a plurality of filters having different pore sizes (within the above range) may be combined to constitute the first filter, and the first filtration may be performed via the first filter. The apertures in this document can be referred to the normal values given by the filter manufacturer. A variety of filters are commercially available, such as from Nihon Pall Ltd., Tokyo Advanced Technology Co., Ltd., and Nihon Entegris KK (formerly known as Nihon Mykrolis, Japan). KK)), and Kitz Micro Filter Corporation.

The second filter may be composed of the same material as the first filter described above.

The filtration through the first filter can treat only the pigment dispersant, and the second filtration can treat the radiation-sensitive color composition obtained by mixing the produced pigment dispersant with other components.

The radiation sensitive color composition of the present invention is suitable for use in various applications such as color filters for solid-state imaging devices, color filters for liquid crystal display devices, printing inks, and inkjet inks.

<Color cured film>

The color cured film obtained by curing the colored composition of the present invention is characterized by high color purity, a large absorption coefficient even in the form of a film layer, and good color fastness (especially heat) Resistance and light stability). When viewed on a white LED that is a backlight, due to color curing The film can give excellent color to the color pixels, so when the color cured film is applied to a liquid crystal display device provided with a white LED, an excellent effect can be obtained, and a color solidified film can be used to form a color filter for a liquid crystal display device. The color pixels on the light sheet.

When a color cured film is formed on any substrate or substrate, the curable color composition may be coated, or the substrate or the like may be immersed into the curable color composition to form a curable color composition layer, and then cured. . When the patterned color cured film is formed, the curable color composition may be coated on the substrate by an inkjet recording process, or may be, for example, by pattern printing or offset printing. A publicly known printing manufacturing method coats a curable color composition on a substrate. From the standpoint of forming a high definition pattern, a preferred method is, for example, forming a curable color composition on a substrate, exposing the curable color composition with light according to a predetermined pattern, and developing the curable color composition layer to move Except for the unexposed part, a detailed description will be given later.

<Method of Manufacturing Color Filter>

The color filter of the present invention uses the above-described curable color composition of the present invention. For example, the color filter comprises a color pattern of one or more colors, preferably three or four colors, which is the use of the curable color composition of the present invention described above on a substrate as described below.

The color filter of the present invention uses the curable color composition of the present invention having a large depth of focus (DOF), thereby reducing residual developer or pattern edge roughness.

The thickness of the color pattern herein is preferably from 0.1 μm to 2.0 μm, more Preferably, it is 0.2 μm to 1.0 μm to form a finer pattern or to prevent adjacent image sensors from receiving light obliquely passing through the color filter.

The method of producing the color filter of the present invention is not particularly limited. For example, a preferred method of manufacturing a color filter includes the steps of: coating the above-described curable color composition of the present invention on a substrate, then exposing the coated coating layer through a mask, and coating the exposure. The cloth layer is developed to form a color pattern. The above steps can be repeated for various colors to form patterns of various colors, thereby producing color filters of three or four colors.

More specific examples of the method of manufacturing the color filter will be described below.

Thus, the method of making a color filter comprises the steps of coating (preferably coating) a curable color composition of the invention on a substrate (optionally followed by pre-baking ( Prebaking) pre-baking the coated curable color composition; exposing the coated curable color composition to the pattern via a mask; and curing the color composition exposed to the pattern using an alkaline developer Development (optionally followed by post-baking of the curable color composition developed with an alkaline developer).

More specifically, the coating step includes, for example, applying the curable color composition of the present invention to a suitable substrate by a spinner or the like to provide a smooth coating layer. The thickness of the dried coating layer is usually from 0.1 μm to 5 μm, preferably from 0.2 μm to 2 μm.

After application of the curable color composition, the curable color composition is typically pre-baked to evaporate the solvent and thereby provide a dried coating layer (pre-baking step). The prebaking step can be carried out by indirect thermal drying with hot air or the like, or direct heating on a hot plate or the like (50 seconds to 200 at about 80 ° C to 140 ° C). Seconds, etc. Prebaking can be carried out by vacuum drying.

Further, post-baking is performed to sufficiently cure the pattern obtained after development, thereby improving the mechanical strength of the pattern and providing a film of fixation (post-baking step). For example, when a color filter of three colors is to be prepared, the initially formed pattern is then subjected to two cycles of applying a resist liquid of another color and then developing and exposing.

Post-baking is to prevent color mixing with the applied resist solution, as well as patterning caused by exposure and development in these cycles. Post-baking is carried out in the same manner as described for prebaking, but post-baking is carried out at a higher temperature for a longer period of time than the pre-baking conditions. For example, post-baking requires indirect heating in an oven at about 180 ° C to 250 ° C for about 0.5 hours to 2 hours, or on a hot plate at about 180 ° C to 250 ° C for about 2 minutes to 10 minutes. Direct heating.

The light source for pattern exposure during the exposure step is not particularly limited. A preferred light source having a significant effect on patternability is light having a wavelength of 410 nm or less, and particularly preferably an i line (365 nm) from a mercury lamp.

The developer for developing the curable color composition is not particularly limited, and a known developer can be used. The developer is, for example, an organic alkaline compound aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydrogen. Tetrapropylammonium oxide, tetrabutylammonium hydroxide, Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene. Among them, the alkaline developer which preferably achieves the object of the present invention is an organic quaternary ammonium salt, which is, for example, tetramethylammonium hydroxide (TMAH).

The substrate of the present invention is not particularly limited, and examples of the substrate that can be used include: a glass substrate, a plastic substrate, an aluminum substrate, a base material of an electronic component (for example, a germanium wafer for a solid-state image sensor, A transparent resin substrate, a resin film, a display surface of a cathode ray tube, a light capturing surface of a camera tube, and a semiconductor wafer on which a solid-state image sensor (CCD, CMOS, BBD, CID, BASIS, etc.) is formed. Further, the substrate may also be used as follows: a contact image sensor using a thin film semiconductor, a liquid crystal display surface, a photoconductor for color electrophotography, and an electrochromic (EC) display device.

In order to improve the adhesion of the color filter layer, it is preferred to treat the substrate by high adhesion. Specifically, the pattern of the curable color composition may be formed after the substrate is previously coated with a thin layer of a decane coupling agent or the like, or a decane coupling agent is previously contained in the curable color composition.

When the step is performed on the substrate, the curable color composition of the present invention may be applied after the planarization layer to remove the step of smoothing the coated surface applied to the substrate.

For example, solid-state image sensors (eg, CCD and CMOS) include: a photoelectric conversion region (photodiode) for generating electrons on a germanium substrate depending on the amount of received light; and a readout gate Zone, which is used for output generation Electronics. The step may occur between the read gate region and the photodiode region because a light shielding layer is formed on the top of the read gate region to protect the read gate region from light, which would otherwise cause noise and hinder accurate data output. There is no light shielding layer in the photodiode area. If a color resist is applied at this step to directly form a color filter, the length of the light path is increased to cause a dark image and poor light collecting ability. In order to improve the above problem, it is preferable to form a transparent planarization layer between the device (for example, CCD or CMOS) and the color filter to achieve the purpose of removing the above steps.

The material of the planarization layer includes a photocurable resist liquid such as the curable color composition of the present invention and a heat curable resin such as an acrylic resin and an epoxy resin.

a color filter film obtained by the method for producing a color filter of the present invention or a color filter film having a color solidified film formed using the curable color composition of the present invention (color filter of the present invention) When displayed, the above can provide vivid color and high contrast, and color durability (especially heat resistance and light stability) is also excellent because the coloring composition of the present invention is used therein. Further, as described later, excellent effects can be provided in good tone reproduction, and this effect can be provided not only when a known CCFL is used as a backlight but also when a white LED is used.

The color filter of the present invention can be applied to a liquid crystal display device and a solid-state image device, and is particularly suitable for a liquid crystal display device. Now, a liquid crystal display device (coated with a color filter containing a dye as a color material) can display an image having excellent color tone, spectral characteristics, and contrast, and the above liquid crystal display device is also suitable for a white LED.

Although the application of the coloring composition of the present invention has been described above focusing on the formation of a color pattern of a color filter, a color composition may be applied to the formation of a black matrix, and a black matrix may be divided into a color pattern of a color filter ( Picture).

A black matrix can be formed on the substrate by using a curable color composition and individual steps of coating, exposure, development, and selective post-baking, the curable color composition comprising a treated pigment of melanin, such as carbon Black or titanium black.

The coloring layer formed by coating the coloring composition of the present invention on a substrate generally has a dry thickness of from 0.3 μm to 5.0 μm, more preferably from 0.5 μm to 3.5 μm, particularly from 1.0 μm to 2.5 μm.

According to any method known in the art, the color filter of the present invention obtained as described above and the G (green) and B (blue) color filters constitute a pixel. The filter has very high transparency, excellent spectral characteristics, and small depolarization, and thus can provide a liquid crystal display device capable of expressing a clean image. A device having a color filter formed therein can also provide a camera module having good spectral characteristics.

The color filter of the present invention can also be used for liquid crystal display elements and solid-state image devices such as CCD and CMOS (including organic CMOS), and the color filter of the present invention is suitable for high definition with more than 1,000,000 pixels. CCD components and CMOS components. The color filter of the present invention is suitable for a liquid crystal display element and a solid-state image device, and is particularly suitable for use in a liquid crystal display element. Since the specific resistance is lowered, even in the case where a metal complex dye is present as a coloring material, a liquid crystal display element to which a color filter is applied is less likely to generate liquid crystal. The alignment error of the molecules, the spectral characteristics and the thermal resistance are excellent, and thus the color tone and display characteristics of the displayed images are excellent.

<Liquid crystal display element>

The color filter of the present invention is characterized by a color pixel having excellent color tone and light stability, and the color filter of the present invention is particularly suitable for use in a liquid crystal display device. The liquid crystal display element to which the above color filter is applied can exhibit high-quality images with good display image hue and excellent display characteristics.

For example, the definition of the display device and the details of each display device are described in an electronic display device (Japanese name Denshi Disupurei Debaisu; Akio Sasaki; Kogyo Chosakai Publishing Co., Ltd.; 1990) Year), display device (Japanese name Disupurei Debaisu; Sumiaki Ibuki; Sangyo Tosho Publishing Co., Ltd.; 1989) and similar publications. For example, a liquid crystal display device is described in the next generation liquid crystal display technology (Japanese name: Jisedai Ekisho Disupurei Gijutu; edited by Tatsuo Uchida; Industrial Survey Publishing Co., Ltd.; 1994). The liquid crystal display device to which the present invention can be applied can be described The various types are, for example, those of the next generation liquid crystal display technology (Japanese name: Jisedai Ekisho Disupurei Gijutu) mentioned above, and are not particularly limited.

The color filter of the present invention is particularly effective in a color TFT liquid crystal display device. For example, a color TFT liquid crystal display device is described in a color TFT liquid crystal display (Japanese name: Kara TFT Ekisho Disupurei; Kyoritsu Shuppan Co., Ltd.; 1996). The invention can also be applied to: wide A liquid crystal display device of a viewing angle, which is, for example, an in-plane switching (IPS) system or a multi-domain vertical alignment (MVA) system, or STN, TN, VA, OCS, FFS, and R-OCB is preferred.

The color filter of the present invention can also be applied to a COA (Color-Filter On Array) system, which is characterized by high brightness and high definition. In the COA type liquid crystal display device, in addition to the above-mentioned common necessities, a color filter layer may be necessary to meet the requirements of the interlayer insulating film, for example, a low dielectric constant and a liquid removal resistance (resistance to removing) Liquid). The color filter of the present invention is obtained by curing the composition of the present invention, and this should contribute to strongly prevent the specific resistance of the liquid crystal molecules from being lowered, and thereby prevent misalignment of liquid crystal molecules (i.e., display characteristics). Deterioration). Therefore, good color purity and color tone will be ensured, and thus a COA type liquid crystal display device having high resolution and good long-term durability can be provided. In order to meet the demand for lowering the dielectric constant, the color filter may be covered with a resin coating.

For a color layer used in a COA type device, it is necessary to form a rectangular via having a side length of about 1 μm to 15 μm or a conduction path in the form of a tilt angle of a side of the square, which is disposed through the conductive path so as to be disposed in the colored layer. The upper ITO electrode is electrically connected to the end of the drive substrate under the colored layer. The size (or side length) of the conduction path is particularly preferably 5 μm, and this has been successfully achieved by the present invention. For example, the modes of these image displays have been described in the latest trends in EL, PDP, LCD displays - technology and market (Japanese name: EL, PDP, LCD Disupurei-Gijutsu to Shijo no Saishin Doko; page 43 of the Research Study Division of Toray Research Center, Inc.; 2001).

The liquid crystal display device of the present invention is composed of the color filter of the present invention, and the liquid crystal display device of the present invention can also be constituted by various components such as an electrode, a polarizing film, a phase difference film, and a backlight. , a spacer and a view angle compensation film. The color filter of the present invention is suitable for a liquid crystal display device composed of these known components. For example, the above components are described in the '94 Liquid Crystal Display Related Materials and Chemicals Market (Japanese name: '94 Ekisho Disupurei Shuuhen Zairyo‧Kemikaruzu no Shijo; CMC Publishing CO., LTD.); 1994 And the current status and future prospects of the liquid crystal related market (Japanese name: 2003 Ekisho Kannren Shijo no Genjo to Shorai Tenbou; Ryokichi Omote; Fuji Chimera Research Institute, Inc.; 2003).

For example, the backlight is described in SID meeting Digest, 1380 (A. Konn et al. 2005) and Display Monthly (Japanese name Gekkann Disupurei), December 18th, pp. 24-24 ( Hiroyasu Shima) and pages 25 to 30 (Takaaki Yagi).

When incorporated in a liquid crystal display element and combined with a known three-wavelength cold cathode tube, the color filter of the present invention can achieve high contrast. By using red, green, and blue LEDs (RGF-LEDs) as backlights, the brightness and color purity of the liquid crystal display device are And color reproducibility can be further improved.

<Solid-state imaging device>

The solid-state image device of the present invention has the above-described color filter for a solid-state image device of the present invention. The architecture of the solid-state imaging device of the present invention is not particularly limited as long as it has the color filter for the solid-state imaging device of the present invention and can function as a solid-state imaging device. The demonstration structure is as follows.

The above structure has, for example, a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (for example, a CCD image sensor, a CMOS image sensor), and a transfer electrode composed of a polysilicon or the like (on the support member) ( Transfer film); a light-shielding film composed of tungsten or the like formed on the photodiode and the transfer electrode to expose only the light-receiving block composed of the photodiode; and protected by a device consisting of tantalum nitride or the like a film formed on the light shielding film to cover the entire surface of the light shielding film and a light receiving block composed of the photodiode; and a color filter for a solid-state image device of the present invention, which is formed on the device protective film.

Other possible architectures include: an architecture having a light condensing unit (for example, a microlens, hereinafter also applicable) on the above protective layer and under the color filter (closer to the support); and color filtering An on-chip architecture with a concentrating unit.

Instance

The following reference examples will make the invention more detailed. Without departing from the spirit of the invention, the materials, usage, ratio, process details, and process steps in the following examples Orders and the like can be arbitrarily modified. Therefore, the scope of the invention should not be construed as being limited by the following examples. In the examples, the "parts" used to describe the usage amount means the "part by weight" of the usage amount unless otherwise specified.

(Synthesis example 1)

Synthesis of Compound (I-a)

The compound (I-a) was synthesized according to the following scheme.

<Synthesis of Compounds (3) and (4)>

A mixture of 100 g of the compound (1) in 200 mL of methanol was stirred at 0 °C. A solution of 124 g of the compound (2) in 100 mL of methanol was added dropwise to the above mixture while maintaining the internal temperature at 10 ° C or lower. Next, 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 28% sodium methoxide in methanol. Next, 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 distilling off the solvent, the mixture was cooled to 0 ° C, and the precipitated crystals were filtered to give 120 g of Compound (4).

<Synthesis of Compounds (5) and (6)>

A solution of 200 g of the compound (4) in 600 mL of N,N-dimethylacetamide was stirred at 0 °C. 191 g of p-toluenesulfonyl chloride was added in four portions while maintaining the internal temperature at 10 ° C or lower, and the mixture was stirred at 0 ° C for 30 minutes. 103 g of pyridine was added dropwise to the mixture while maintaining the internal temperature at 10 ° C or lower, and the mixture was further stirred for one and a half hours. This reaction solution was poured into water (1.5 L) in an ice bath, and the precipitated crystals were filtered to give Compound (5). To the stirred mixture of the obtained compound (5) in 1 L of methanol, 103 g of pyridine was added. The reaction solution was heated under reflux for 1 hour, then cooled to 0 ° C, and the obtained crystal was filtered to give 92 g of Compound (6).

<Synthesis of Compound (7)>

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

<Synthesis of Compound (I-a)>

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

(Synthesis Examples 2 to 4)

Compounds (I-b), (I-d) and (I-h)

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

(Synthesis example 2)

Synthesis of Compound (I-k)

The compound (I-k) was synthesized according to the following scheme.

<Synthesis of Compound (8)>

Phosphorus oxychioride (11.3 g) was added dropwise while stirring at 0 ° C in dimethylformamide (15 mL) while maintaining the internal temperature at 5 ° C or lower, and the mixture was at 0 ° C. The mixture was stirred for one hour to prepare a formazan. To a solution of the compound (6) (10 g) dissolved in dimethylformamide (30 mL), a methylating agent was added dropwise while maintaining the internal temperature at 5 ° C or lower, and the mixture was at 0 ° C. Stir for one hour. Next, the reaction temperature was raised to room temperature, and the mixture was further stirred for one hour. The reaction solution was extracted with water (50 mL) and ethyl acetate (50 mL) and partitioned between them. The resulting organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution (50 mL) and then evaporated. The solvent of the obtained organic layer was evaporated under reduced pressure to give a white solid. Acetone (50 mL) was added to this white solid, and the mixture was stirred and filtered to give compound (8) (7g).

<Synthesis of Compound (9)>

Compound (9) was synthesized according to the route described below.

<Synthesis of Compound (9b)>

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

<Synthesis of Compound (9c)>

35.3 g of hydrazine hydrochloride was added to a mixture of 95 g of the compound (9b) in 500 mL of methanol 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. 100 mL of hydrochloric acid was added dropwise to the above reaction solution, and the precipitated crystals were filtered to obtain 152.9 g of the compound (9c).

The subsequent procedure is carried out in the same manner as described for the compound (6), and the compound (9) is synthesized by substituting the compound (9c) as a starting material to synthesize the compound (9).

<Synthesis of Compound (10)>

A mixture of the compound (8) (5 g) and the compound (9) (5.2 g) in methanol (15 mL) was stirred. Acetic acid (15 mL) was added dropwise to the above mixture, and the mixture was heated to reflux at 70 ° C for 3 hr. The reaction solution was cooled to room temperature, and after filtration and crystallization, Compound (10) (8 g) was obtained.

<Synthesis of Compound (I-k)>

A mixture of 5 g of compound (10), tetrahydrofuran (25 mL) and N-methylpyrrolidone (25 mL) was stirred at room temperature. Zinc acetate dihydrate (1.6 g) was added to the above mixture, and the mixture was stirred at 70 ° C for two hours. Then, the mixture was cooled to room temperature, and the obtained solid was filtered to give Compound (I-k) (3.5 g).

(Evaluation)

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

<heat resistance>

In a TG/DTA analyzer (STIEXSTAR 6000 from SII Nanotech Co., Ltd. (currently Hitachi High-Technologies Inc.), each of the obtained compounds was heated from 40 ° C to 600 ° C at 10 ° C / min, and the decomposition temperature thereof was measured. Evaluation based on the following criteria.

A: The compound decomposes when it exceeds 300 ° C or never decomposes.

B: The compound decomposes at less than or equal to 300 ° C and above 200 ° C.

C: The compound decomposes at less than or equal to 200 °C.

<volatile>

In a TG/DTA analyzer (STIEXSTAR 6000 from SII Nanotech Co., Ltd. (currently Hitachi High-Technology Co., Ltd.), each of the obtained compounds was heated from 40 ° C to 600 ° C at 10 ° C / min, and the weight loss was measured. Evaluation based on the following criteria.

A: The weight loss is less than 10% at less than or equal to 400 °C.

B: The weight loss is greater than or equal to 10% and less than 30% at less than or equal to 400 °C.

C: The weight loss is greater than or equal to 30% at less than or equal to 400 °C.

<solvent resistance>

Each of the obtained compounds was evaluated by the method described in the solvent-resistant exudative portion of JIS K 5101-1991 15.

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

Comparative Compound A: A compound described in the examples in JP-A 2007-100061.

Comparative Compound B: as described in the example of Japanese Patent No. 3750208 The compound described.

Comparative Compound C: a methine coloring matter which is a Zn non-complexation compound (Compound 7) of Compound (I-a).

The above table shows that the compounds in the examples are excellent in heat resistance and volatility. However, Comparative Examples 1 to 3 appeared to be inferior in at least one of heat resistance and volatility.

(Example 101: Manufacturing of color filter)

<Preparation of a resist liquid for a planarization layer>

The following ingredients were mixed in a stirrer to prepare a resist liquid for the planarization layer.

[Components of the resist liquid for the planarization layer]

Benzyl methacrylate/methacrylic acid copolymer (=70/30 [mole 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 starter as shown below: 0.3 parts by weight

<Manufacture of flattened wafer>

The resist liquid used for the planarization layer obtained above is uniformly coated on a six-inch wafer by spin coating to form a coating layer, and the resulting coating layer is heated on a hot plate to The surface temperature was 120 ° C for 120 seconds. The spin coating rate here was controlled to obtain a coating layer having a thickness of about 1 μm after heat treatment. After the heat treatment, the coating layer was further treated in an oven at 220 ° C for one hour to cure the coating layer to form a planarization layer. Flattening with a planarization layer on a six-inch wafer can be obtained from the above Wafer.

<Preparation of color resist liquid (curable color composition)>

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

[Component of color resist liquid]

Benzyl methacrylate/methacrylic acid copolymer (=70/30 [mole ratio]): 3.27 parts by weight

Compound (I-h): 6.65 parts by weight

Polymer dispersant (pigment dispersant obtained from BYK Chemical under Disperbyk-170): 2.56 parts by weight

Propylene glycol monomethyl ether acetate: 81 parts by weight

IRGACURE OXE01 (light initiator from BASF): 1.65 parts by weight

P-methoxyphenol (polymerization inhibitor): 0.002 parts by weight

ARONIX M-305 (polymerizable compound from East Asia Synthetic Co., Ltd.): 1.47 parts by weight

Polymerizable compound as shown below: 3.42 parts by weight

(all n total 12)

<Manufacture of color filters>

The color resist obtained above is uniformly coated on the planarization layer of the planarization wafer by spin coating to form a coating layer, and the resulting coating layer is heated. The plate was heated (prebaked) to a surface temperature of 100 ° C for 120 seconds to form a colored resist layer. The spin coating rate here was controlled to obtain a coating layer having a thickness of about 0.8 μm after the heat treatment.

Next, an i-line stepper (FPA-3000i5+ from Canon Co., Ltd.) was used to expose the color resist layer in the pattern through the mask described below.

The above pattern exposure was performed in the form of a matrix having 21 rows and 19 columns in a total of 399 cells.

The selected condition is a minimum starting dosage of 500J / m ^2, 21 to each successive increment of exposure dose column 250J / m ^2.

The conditions selected were also from the best focal length assigned to the center (focusing 0.0 μm), and the focal length was changed to 0.1 μm for each successive 19 lines. Specifically, the focal length is changed for each successive line from the best focal length assigned to the center line.

The reticle used has a mask pattern in which six sizes of square pixel patterns (1.0 μm square, 1.5 μm square, 2.0 μm square, 3.0 μm square, 4.0 μm square, and 7.0 μm square) are arranged. In a region of 4 μm × 3 μm.

The colored resist exposed to the pattern was developed by the Puddle method for 60 minutes at room temperature using an organic alkaline developer CD-2060 (from Fujifilm Electronic Materials). Thereafter, it was rinsed with a pure water rotary shower for 20 seconds and then washed with pure water. Next, the water droplets were removed by high pressure air and the substrate was air dried to obtain a color pattern. Thereby, a color filter is obtained.

The color filter described above is used in a solid-state image sensor and a liquid crystal display device, and both exhibit excellent performance.

Claims (18)

a pigment represented by formula (I): In the formula (I), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; M represents a monovalent to trivalent metal; L represents an anion or a ligand capable of coordinating to a metal; m represents 1 to An integer of 3; and n represents an integer from 0 to 2; the group included in the parentheses forms a monovalent anion as a unitary group. The dye according to claim 1, wherein in the above formula (I), R ³ and R ⁴ each independently represent an alkyl group having 1 to 5 carbon atoms. The dye according to claim 1 or 2, wherein in the above formula (I), R ¹ and R ² each independently represent an alkyl group, an aryl group or a heterocyclic group. The dye according to claim 1 or 2, wherein in the above formula (I), R ¹ and R ² are the same group, and R ³ and R ⁴ are the same group. The pigment according to the first or second aspect of the invention, wherein the pigment has a fifth-order anti-solvent exudation property, which is evaluated according to the absolute comparison method of JIS K 5101-1991 15. The pigment described in claim 1 or 2, wherein In the formula (I), n is 0. The dye according to the above-mentioned item (1), wherein the compound represented by the above formula (I) is a compound represented by the following formula (IA): In the formula (IA), R ¹ to R ⁴ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aminomethyl group, an alkoxy group, an amine group, a sulfonamide, a sulfonate or a group of a hydrazine or a cyano group; each of R ⁵ independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and M' represents a divalent metal atom; the groups included in the parentheses each form a monovalent anion as a whole group . The dye according to claim 1 or 2, wherein M in the above formula (I) and M' in the above formula (I-A) represent zinc. The dye according to the first or second aspect of the invention, wherein the compound represented by the above formula (I) is any one of the compounds represented by the following formulas (Ia) to (In): In the formula (If) and the formula (Il), Me represents a methyl group. The pigment according to claim 1 or 2, wherein the compound represented by the above formula (I) has a molecular weight of 500 to 1200. A pigment dispersing agent comprising at least one of the pigments as described in any one of claims 1 to 10. A color composition comprising at least one pigment as described in any one of claims 1 to 10. A curable color composition comprising at least one pigment as described in any one of claims 1 to 10. A radiation-sensitive color composition comprising at least one of the pigments of any one of claims 1 to 10. A color filter formed by using a curable color composition as described in claim 13 of the patent application. An ink for ink jet printing using the color composition as described in claim 12 of the patent application. A solid-state image sensor or a liquid crystal display device comprising the color filter of claim 15. A method of manufacturing a color filter, comprising: applying a curable color composition as described in claim 13 of the patent application to a substrate; and coating the curable color composition through a mask Exposing in the pattern; and developing the curable color composition exposed to the pattern using an alkaline developer.