TW201542708A - Dye and colored curable resin composition - Google Patents

Abstract

The present invention relates a dye having a group containing silicon atom, and having squarylium skeleton.

Description

Dye and color hardening resin composition

The present invention relates to a dye and a color hardening resin composition.

The squaraine dye is used in the field of photographic photoreceptors and the like. In the Japanese Patent Publication No. Sho 60-248652, the squarylium dye is a compound represented by the formula (II-0).

The present invention includes the following inventions.

[1] A dye containing a ruthenium-containing group and containing a squaraine skeleton.

[2] The dye according to [1], wherein the group containing a ruthenium atom is a group containing -Si(R ¹⁴ ) ₃

[R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the three R ^{14 's} may be the same or different).

[3] The dye according to [1] or [2], wherein the group containing a halogen atom is a group represented by the formula (iia) [In the formula (iia), R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The three R ^{14 's} may be the same or different. L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. The -CH ₂ - contained in the alkanediyl group may also be substituted with an oxygen atom. * indicates a bond base].

[4] The dye according to any one of [1] to [3], which is a compound represented by the formula (IIa) [In the formula (IIa), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (constituting the saturated hydrocarbon group) Between the carbon atoms, an oxygen atom or a sulfur atom can also be inserted.

R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxyl group.

R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a ruthenium atom-containing group, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting the saturated hydrocarbon group) A phenyl group which may have an oxygen atom or a sulfur atom or may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a halogen atom].

[5] The dye according to [4], wherein the group containing a ruthenium atom is a group represented by the formula (iia) [In the formula (iia), R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The three R ^{14 's} may be the same or different. L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. The -CH ₂ - contained in the alkanediyl group may also be substituted with an oxygen atom. * indicates a bond base].

[6] The dye according to any one of [4], wherein the phenyl group which may have a substituent is a group represented by the formula (i): (In the formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5. When m is 2 or more, The plural R ¹² may be the same or different, and * represents a group bonded to a nitrogen atom).

[7] The dye according to any one of [1] to [6], which is a compound represented by the formula (II): [In the formula (II), R ^1a and R ^2a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting the saturated hydrocarbon group) An oxygen atom or a sulfur atom can be inserted).

R ^3a and R ^4a each independently represent a hydrogen atom or a hydroxyl group.

One of R ^5a and R ^6a is a group represented by the formula (ii), and the other is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (a carbon atom constituting a saturated hydrocarbon group) It is also possible to insert an oxygen atom or a sulfur atom or a group represented by the formula (i).

(In the formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5. When m is 2 or more, The plural R ¹² may be the same or different, and * represents a group bonded to a nitrogen atom.

(In the formula (ii), n represents an integer of 1 to 8; R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * represents a bond with a nitrogen atom; Base. Three R ¹⁴ can be the same or different.)]

[8] A coloring agent comprising the dye according to any one of [1] to [7].

[9] The coloring agent according to [8], which further contains a yellow pigment.

[10] The coloring agent according to [9], wherein the yellow pigment is at least one pigment selected from the group consisting of C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 150, and C.I. Pigment Yellow No. 185.

[11] A coloring-curable resin composition, which comprises the coloring agent according to any one of [8] to [10], a resin, a polymerizable compound, and a polymerization initiator.

[12] A coating film formed from the colored curable resin composition according to [11].

[13] A color filter formed of the colored curable resin composition according to [11].

[14] A display device comprising the color filter of [13].

The dye of the present invention is excellent in solubility in an organic solvent, and a color filter formed of a colored curable resin composition containing the dye is also excellent in heat resistance.

The present invention is a dye having a ruthenium atom-containing group and having a squaraine skeleton.

Examples of the group containing a halogen atom include a substituent having a decyloxy group such as a trialkylphosphonium group or a trialkoxyfluorenyl group.

The trialkyl decyloxy group may, for example, be a trialkyl decyloxy group having a C 1 to 8 (preferably 1 to 4) alkyl group, such as a trimethyl decyloxy group or a triethyl decyloxy group.

The trialkoxyfluorenyl group may, for example, be a trialkylsulfonyl group having an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4), such as a trimethoxyindenyl group or a triethoxyfluorenyl group.

A group having a decyloxy group, which may be, for example, an alicyclic ring having a carbon number of 3 to 10. a group of a hydrocarbon and a decyloxy group, and a group having a group of an oxygen atom and a sulfur atom and a decyloxy group in a saturated hydrocarbon group having 1 to 20 carbon atoms which will be described later, and such a group may further contain a halogen atom or an alkyl group. An amine group and a dialkylamine group (hereinafter, collectively referred to as such a substituted amine group is a "(di)alkylamino group").

In the dye of the present invention, the group containing a halogen atom is preferably a group containing -Si(R ¹⁴ ) _{3 , and} the group represented by the formula (iia) is more preferably:

In -Si(R ¹⁴ ) ₃ , R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The three R ^{14 's} may be the same or different.

The alkyl group represented by R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group.

The alkoxy group represented by R ¹⁴ may, for example, be a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

R ^{14 is} preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group. Preferably, a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group is more preferably.

It is preferable that three R ¹⁴ are the same.

In the formula (iia), R ¹⁴⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. The -CH ₂ - contained in the alkanediyl group may also be substituted with an oxygen atom. * indicates a bond group with a nitrogen atom.

The alkyl group represented by R ¹⁴⁴ may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group.

Examples of the alkoxy group represented by R ¹⁴⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

R ^{144 is} preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group, and more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group. Three R ¹⁴⁴ are preferred.

The alkanediyl group represented by L ¹ may, for example, be a methylene group, an ethylidene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group or a butane- 1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl and the like.

L ^{1 is} preferably a C 2 to 4 alkanediyl group.

The group represented by the formula (iia) includes the groups shown below. Among them, a group represented by the formula (ii-1) to a group represented by the formula (ii-6) is preferred.

(* indicates a bond to a nitrogen atom or a carbon atom).

The dye of the present invention may, for example, have a trimethyl group. A dye having a squaraine skeleton of a decyloxy group such as a decyloxy group, a triethyl decyloxy group, a trimethoxy fluorenyl group or a triethoxy fluorenyl group.

The dye of the present invention contains a compound represented by formula (IIa) (hereinafter, it is also described as the compound (IIa)), and a compound represented by the formula (II) (hereinafter also referred to as the compound (II)) is more preferable. Compound (IIa) and compound (II) also contain their tautomers, respectively.

[In the formula (II), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (constituting the saturated hydrocarbon group) Between the carbon atoms, an oxygen atom or a sulfur atom can also be inserted.

R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxyl group.

R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a ruthenium atom-containing group, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting the saturated hydrocarbon group) A phenyl group which may have an oxygen atom or a sulfur atom or may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a halogen atom. ]

[In the formula (II), R ^1a and R ^2a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting the saturated hydrocarbon group) An oxygen atom or a sulfur atom can be inserted).

R ^3a and R ^4a each independently represent a hydrogen atom or a hydroxyl group.

One of R ^5a and R ^6a is a group represented by the formula (ii), and the other is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting a saturated hydrocarbon group, An oxygen atom or a sulfur atom or a group represented by the formula (i) may also be inserted.

(In the formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5. When m is 2 or more, The plural R ¹² may be the same or different, and * represents a group bonded to a nitrogen atom.

(n, R ¹⁴ and *, the same as defined above.)]

In the present specification, 2 ^♁ indicates that the ring has a positive valence of two valences.

Examples of the halogen atom of the formula (IIa) and the formula (II) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The monovalent saturated hydrocarbon group in the formula (IIa) and the formula (II) may, for example, be 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 or a dodecyl group. a linear alkyl group having 1 to 20 carbon atoms such as an alkyl group, a hexadecyl group or an eicosyl group; an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, an isopentyl group, and a new a branched chain alkyl group having a carbon number of 3 to 20 such as a pentyl group and a 2-ethylhexyl group; a carbon number of 3 to a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group; 20 alicyclic saturated hydrocarbon groups.

Examples of the substituent of the monovalent saturated hydrocarbon group in the formula (IIa) and the formula (II) include a halogen atom, a hydroxyl group, and a (di)alkylamino group having 1 to 8 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The (di)alkylamino group may, for example, be a methylamino group, an ethylamino group, a n-propylamino group, a n-butylamino group, a n-pentylamino group, a dimethylamino group or a diethylamino group. , dipropylamino group, ethylmethylamino group and the like.

Examples of the above-mentioned saturated hydrocarbon group which may have a substituent include, for example, a group represented by the following formula (* indicates the basis of the bond).

In the formula (IIa) and the formula (II), a group in which an oxygen atom or a sulfur atom is interposed between carbon atoms constituting the monovalent saturated hydrocarbon group may, for example, be a group represented by the following formula: (* indicates the basis of the bond).

R ¹ , R ² , R ^1a , R ^2a , R ¹¹¹ and R ^{112 are} each independently a hydrogen atom, a hydroxyl group and an alkyl group having 1 to 4 carbon atoms; a hydrogen atom, a hydroxyl group and a methyl group are more preferable; The atom is better.

In the compound (IIa), at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ represents a group containing a halogen atom. Preferably, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group represented by the formula (iia); and at least one of R ⁵ and R ⁶ is a group represented by the formula (iia), R ^It is more preferable that at least one of ¹⁵ and R ¹⁶ is a group represented by the formula (iia).

In the compound (IIa), the group containing a halogen atom is preferably a group represented by the formula (iia), and the group represented by the formula (ii) is more preferably.

In the compound (IIa), a phenyl group which may have a substituent is preferably a group represented by the formula (i).

The compound (IIa), wherein the phenyl group having a ruthenium atom is a group represented by the formula (iia), and the phenyl group which may have a substituent is a group represented by the formula (i) (hereinafter, the compound has It is more preferably referred to as "compound (IIb)").

In the compound (II), one of R ^5a and R ^6a is a group represented by the formula (iia), and the other is a hydrogen atom, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( It is preferred that the carbon atom constituting the saturated hydrocarbon group may be inserted into an oxygen atom or a sulfur atom or a group represented by the formula (i); and one of R ^5a and R ^6a is a group represented by the formula (ii), The other one is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (a carbon atom or a sulfur atom may be interposed between carbon atoms constituting a saturated hydrocarbon group) or a group represented by the formula (i). Better.

R ⁵ , R ⁶ , R ^5a , R ^6a , R ¹⁵ and R ¹⁶ may have a substituent of a phenyl group, and examples thereof include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and a monovalent carbon number of 2 to 20 carbon atoms. Saturated hydrocarbon group.

The monovalent saturated hydrocarbon group in the substituent is: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, 2 Alkyl groups having 1 to 20 carbon atoms such as ethylhexyl, n-octyl, n-decyl, n-decyl, n-undecylalkyl and n-dodecyl are preferred.

Examples of the monovalent unsaturated hydrocarbon group in the substituent include a carbon such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a nonenyl group. Number of 2 to 20 alkenyl groups.

In the formula (i), examples of the monovalent unsaturated hydrocarbon group represented by R ¹² include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, and a decene group. An alkenyl group having 2 to 20 carbon atoms such as a decyl group or a decyl group.

Examples of the monovalent saturated hydrocarbon group represented by R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. An alkyl group having 1 to 20 carbon atoms such as n-heptyl, 2-ethylhexyl, n-octyl, n-decyl, n-decyl, n-undecylalkyl or n-dodecylalkyl.

R ¹² is preferably a hydrogen atom or a carbon number of 1 to 4, more preferably a hydrogen atom, a methyl group or an ethyl group.

The group represented by the formula (i) may be exemplified by the following groups: (* indicates the group bonded to the nitrogen atom).

In the formula (II), n is preferably an integer of 1 to 6, and 1 to 4 The integer is better.

When the groups represented by R ⁵ , R ⁶ , R ^5a and R ^6a represent a group other than the group represented by the formula (iia) and the formula (ii), respectively, a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, The group represented by the formula (i) is preferred, and the hydrogen atom is more preferred.

Base shown by (R ⁵ and R ⁶ each have the same meaning as defined above, * represents a bond to a carbon atom), and The groups shown (R ^5a and R ^6a respectively represent the same meaning as described above, and * represents a bond group with a carbon atom), and the following groups and the like are exemplified:

a dye containing a ruthenium-containing group and containing a squaraine skeleton The compound represented by the formula (AII-1) to the compound represented by the formula (AII-75) can be mentioned.

In the present invention, from the point of easy availability of raw materials, The compound represented by the formula (AII-4) to the compound of the formula (AII-6) and the compound of the formula (AII-31) to the compound of the formula (AII-33) are preferred.

Compound (II), according to JP-A-2002-363434 It is produced by the method described in the publication, specifically, by the compound represented by the formula (IV-1) and squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) ( 3,4-dihydroxy-3-cyclobutene-1,2-dione) was produced by reaction.

(wherein R ^1a to R ^6a represent the same meaning as described above, respectively).

Relative to the compound of formula (IV-1), 1 mole, squaric acid The amount used is preferably 0.5 mol or more and 0.8 mol or less, and more preferably 0.55 mol or more and 0.6 mol or less.

The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 80 ° C to 140 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 3 hours to 8 hours.

From the point of productivity, the reaction is in an organic solvent It is better to carry out. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; and nitrohydrocarbon solvents such as nitrobenzene; A ketone solvent such as isobutyl ketone; a guanamine solvent such as 1-methyl-2-pyrrolidone; and the like may be used in combination. Among them, a mixed solvent of butanol and toluene is preferred. The amount of the organic solvent to be used is preferably 30 parts by mass or more and 200 parts by mass or less based on 1 part by mass of the compound represented by the formula (IV-1), and more preferably 50 parts by mass or more and 150 parts by mass or less.

The method of obtaining the compound (II) of the objective compound from the reaction mixture is not particularly limited, and various conventional methods can be employed. For example, a method of filtering out precipitated crystals after cooling can be carried out. The crystals to be collected are washed with water or the like, and then dried. Further, it may be further refined in a conventional manner such as recrystallization, as needed.

<colorant>

The coloring agent of the present invention contains a dye having a ruthenium atom-containing group and having a squaraine skeleton (hereinafter, this coloring agent is referred to as "coloring agent (A)").

The coloring agent (A), in addition to the dye of the present invention, may further contain other dyes (A2), pigments (P), or mixtures thereof for color adjustment, that is, to adjust the spectral characteristics.

Examples of the dye (A2) include oil-soluble dyes, acid dyes, and acid dyes. Dyes such as amine salts and sulfonamide derivatives of acid dyes, such as those classified as dyes in the colour index (published by The Society of Dyers and Colourists), and dyeing notes (color dyeing) Conventional dyes. Further, examples of the chemical structure include a coumarin dye, a gold-containing azo dye, a pyridone azo dye, a barbiturate azo dye, a quinoline yellow dye, a methine dye, an anthocyanin dye, and an anthracene. Anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and anthraquinone dyes. These dyes may be used singly or in combination of two or more.

Specifically, for example, CI Solvent Yellow No. 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), No. 14, No. 15, No. 23, No. 24, No. 38, No. 62, No. 63, No. 68 , 82, 94, 98, 99, 162; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI solvent dye; CI Acid Yellow No. 1, No. 3 , 7, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76 No., 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196 , 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240 No., No. 242, No. 243, 251 No. 6; Acidic Orange 6, No. 6, No. 8, No. 10, No. 12, No. 26, No. 50, No. 51, No. 52, No. 56, No. 62, No. 63, No. 64, No. 74, No. 75, No. 75, 94, 95, 107, 108, 169, 173; CI dyes, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43 and 47, 50, 54, 54, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136 , No. 138, No. 141; CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96 No., No. 97, No. 106, No. 107; such as CI direct dye, CI mediated yellow No. 5, No. 8, No. 10, No. 16, No. 20, No. 26, No. 30, No. 31, No. 33, No. 42, No. 43 No., No. 45, No. 56, No. 61, No. 62, No. 65; CI mordant orange No. 3, No. 4, No. 5, No. 8, No. 12, No. 13, No. 14, No. 20, No. 21, No. 23, No. 24, No. 28, No. 29, No. 32, No. 34, No. 35, No. 36, No. 37, No. 42, No. 43, No. 47, No. 48; etc. CI mordant dyes.

In the case of the dye (A2), a yellow dye such as a coumarin dye, a gold-containing azo dye, a pyridone azo dye, a barbiturate azo dye, a quinoline yellow dye, a methine dye, an anthocyanin dye, or the like is used. Preferably.

The content of the dye of the present invention is usually from 3 to 99.9% by mass, more preferably from 4 to 50% by mass, based on the total amount of the coloring agent, 5 It is even better to 30% by mass. When the content of the dye of the present invention is within the above range, the brightness at the time of forming a color filter is high, and therefore it is preferable.

The pigment (P) is not particularly limited, and conventional use can be used. Pigments, for example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists).

Examples of the pigment (P) include: CI Pigment Yellow No. 1, No. 3, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 20, No. 31, No. 31, No. 53, 83 No., 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, Yellow pigments such as No. 166, No. 173, No. 194, No. 214; CI Pigment Orange No. 13, No. 31, No. 36, No. 38, No. 40, No. 42, No. 43, No. 51, No. 55, No. 59, No. 61 , orange pigments such as No. 64, No. 65, No. 71, No. 73; and green pigments such as CI Pigment Green No. 7, No. 36 and No. 58.

Pigment (P), CI Pigment Yellow No. 1, No. 3, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 20, No. 23, No. 31, No. 53, No. 83, No. 86 , 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 No. 194, No. 214 and other yellow pigments; and CI Pigment Green No. 7, No. 36, No. 58 and other green pigments are preferred, CI Pigment Yellow No. 138, No. 150, No. 185 and CI Pigment Green No. 36, No. 58 For better, CI Pigment Yellow No. 138, CI Pigment Yellow No. 150 and CI Pigment Yellow No. 185 is even better. By containing the above pigment, the transmission spectrum can be easily optimized, and the color resistance and chemical resistance of the color filter are excellent.

<Coloring curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). Further, it may contain a solvent (E).

In the present specification, the compounds of the respective components may be used singly or in combination of plural kinds unless otherwise specified.

In the color hardening resin composition of the present invention, relative The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, still more preferably from 10 to 50% by mass, based on the total amount of the solid component. When the content of the coloring agent (A) is within the above range, the color density at the time of forming the color filter is sufficient, and the desired amount of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that it can be formed. A model with sufficient mechanical strength. Here, the "total amount of solid component" in the present specification means the amount by which the solvent content is removed from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative to the total amount of the solid component can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, and an alkali-soluble resin is preferred. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Ba) (hereinafter sometimes referred to as "(Ba)") and a carbon ether having a carbon number of 2 to 4 And an ethylenically unsaturated bond monomer (Bb) (hereinafter sometimes referred to as Copolymer of "(Bb)"); resin [K2]: (Ba), (Bb), monomer (Bc) copolymerizable with (Ba) (unlike (Ba) and (Bb)) ( Hereinafter, a copolymer sometimes referred to as "(Bc)"); a resin [K3]: a copolymer of (Ba) and (Bc); a resin [K4]: a copolymer of (Ba) and (Bc) and (Bb) Reactive resin; resin [K5]: a resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba); a resin [K6]: reacting a copolymer of (Bb) and (Bc) with (Ba) And a resin which reacts with a carboxylic acid anhydride.

(Ba) may, for example, be an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and citric acid Acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrogen Unsaturated dicarboxylic acid such as phthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxyl group Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2 - alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6 a carboxyl group-containing bicyclic unsaturated compound such as ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4- Vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydration 5, Unsaturated dicarboxylic anhydride such as 6-dicarboxybicyclo[2.2.1]hept-2-ene; succinic acid mono[2-(methyl)-propyl Acyl oxy ethyl] phthalate, mono An unsaturated mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid of 2 or more elements such as [2-(meth)acryloxyethyl)]; An α-(hydroxymethyl)acrylic acid or the like, an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferred from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(Bb) means, for example, a cyclic ether structure having a carbon number of 2 to 4. A polymerizable compound (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.

(Bb) A monomer having a cyclic ether and a (meth)acryloxy group having 2 to 4 carbon atoms is preferred.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl) and "(meth)acrylate" have the same meaning.

(Bb) can be exemplified by having an oxirane group and an ethylene group. a monomer having a saturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

In order to make the color filter of the obtained color filter more reliable, such as heat resistance and chemical resistance, (Bb) is preferably a monomer containing an oxirane group and an ethylenically unsaturated bond.

(Bc) may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, or tert-butyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-ester (in the technical field thereof) The customary name is "dicyclopentanyl (meth)acrylate". Also, it is sometimes called "tricyclodecyl (meth)acrylate), tricyclo(meth)acrylate [5.2.1.0 ^2,6 Terpene-8-ester (in the technical field, the conventional name is "dicyclopentenyl (meth)acrylate)", dicyclopentanyloxyethyl (meth)acrylate, (meth)acrylic acid Anthracene ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (methyl) (meth) acrylate such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate Hydroxy-containing (meth) acrylate such as 2-hydroxypropyl (meth)acrylate; dicarboxylic acid such as diethyl maleate, diethyl fumarate or diethyl itaconate Diester; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1 Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxydi Ring [2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo [2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2 - alkene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl -5-Methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-benzyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]g 2-ene, 5,6-double (cyclohexene) a bicyclic unsaturated compound such as a bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzoic acid N-Succinimide, N-Amber succinimide-3-methyleneimine benzoate, N-Amber succinimide-4-methyleneimine butyric acid Ester, N-succinimide-6-methyleneimide hexanoate, N-succinimide-3-oxenimide propionate, N-(9-propylene Mercapto) dicarbonyl ruthenium derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxybenzene Ethylene, acrylonitrile, methacrylonitrile, ethylene chloride, vinyl chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3- Dimethyl-1,3-butadiene and the like.

Among these, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide, N are used in terms of copolymerization reactivity and heat resistance. - Benzyl maleimide, bicyclo [2.2.1] hept-2-ene, etc. are preferred.

The resin (B) may, for example, be a (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer or an acrylic-3,4-epoxytricyclo[5.2.1.0 ^2,6 Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, (meth) acrylate ring Oxypropyl propyl ester / styrene / (meth) acrylic acid copolymer, acrylic acid -3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester / (meth) acrylate / N-cyclohexyl cis-butene a resin such as a quinone imine copolymer, a 3-methyl-3-(meth) propylene methoxymethyl oxetane/(meth)acrylic acid/styrene copolymer [K2]; (meth)acrylic acid Resin such as benzyl ester/(meth)acrylic acid copolymer, styrene/(meth)acrylic copolymer, etc. [K3]; benzyl (meth)acrylate/(meth)acrylic acid copolymer addition (methyl) Acrylic propyl acrylate resin, tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer addition (meth)acrylic acid propyl acrylate resin, trimethyl sulfonium (meth) acrylate Ester/benzyl (meth)acrylate/(meth)acrylic acid copolymer addition to glycidyl (meth)acrylate Resin such as resin [K4]; copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate and (meth)acrylic acid, tricyclodecyl (meth)acrylate/benzene Resin such as copolymer of ethylene/glycidyl (meth)acrylate and resin reacted with (meth)acrylic acid [K5]; copolymerization of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate A resin such as a resin which reacts with (meth)acrylic acid and a resin which reacts with tetrahydrophthalic anhydride, such as a resin [K6].

Among them, the resin (B) is preferably a resin [K1] and a resin [K2].

Resin [K1], please refer to the document "Experimental Method of Polymer Synthesis" (Dazu Long, Issuer Chemicals Co., Ltd., 1st edition, 1st brush, issued on March 1, 1972) and in the literature. Manufactured from the cited documents.

The obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by reprecipitation or the like may be used. In particular, in the solvent for the polymerization, the solution after the reaction can be used as it is to prepare the colored curable resin composition of the present invention by using the solvent contained in the colored curable resin composition of the present invention. The manufacturing steps of the colored curable resin composition of the present invention can be simplified.

The weight average molecular weight of the polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter can be increased, the film residual ratio can be improved, the solubility of the unexposed portion to the developer can be improved, and the resolution of the coloring pattern tends to be improved.

The molecular weight distribution "weight average molecular weight (Mw) / number average molecular weight (Mn)" of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. Here, the measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B) in the acid value can be determined, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When the content of the resin (B) is within the above range, a color pattern can be formed, and the resolution of the coloring pattern and the film residual ratio tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a living radical- and/or acid-polymerizable compound which can be produced from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, etc., and The acrylate compound is preferred.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Alcohol five (a Acrylate, dipentaerythritol hexa(meth) acrylate, tripentenol octa (meth) acrylate, tripentyltetraol hexa(meth) acrylate, tetrapentaerythritol (Meth) acrylate, tetrapentaerythritol 九(meth) acrylate, 1,3-isocyanate (2-(methyl) propylene oxyethyl) ester, ethylene glycol modified pentylene Alcohol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol Hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like.

Among them, dinonpentaerythritol penta (meth) acrylate and dine pentaerythritol hexa (meth) acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is 150 It is better to 2,900 and 250 to 1,500 is better.

The content of the polymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the film residual ratio at the time of formation of the coloring pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is an active radical, an acid or the like which can be generated by the action of light or heat, and a conventional polymerization initiator can be used. Examples of the polymerization initiator which generates a living radical include, for example, an O-indenyl hydrazine compound, an alkyl phenone compound, and three a compound, a mercaptophosphine oxide, and a biimidazole compound.

Examples of the above O-indenyl hydrazine compound include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoic acid.醯oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4- Dioxycyclopentylmethyloxy)benzimidyl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl- 6-(2-Methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl -6-(2-Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE 01, OXE 02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Wherein, the O-indenyl hydrazine compound is selected from the group consisting of: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoic acid醯oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylsulfanylphenyl) At least one selected from the group consisting of -3-cyclopentylpropan-1-one-2-imine is preferred, N-benzylidene-1-(4-phenylsulfanylphenyl) octyl Alkan-1-one-2-imine is more preferred. In the case of these O-indenyl compounds, there is a tendency to produce a high-intensity color filter.

Examples of the alkylphenone compound include 2-methyl-2-N-morpholinyl-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamine. 1-(4-N-morpholinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- 1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2- Methyl-1-[4-(2-hydroxyethoxy) Oligomers of phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α, --diethoxyacetophenone, benzyldialdehyde, and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

The aforementioned three Examples of the compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three. , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

As the above mercaptophosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like can also be used. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation).

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204) The imidazole compound in which the phenyl group at the 4, 4', 5, 5'-position is substituted with a carbon alkoxy group (see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.).

Further, the polymerization initiator (D) may be exemplified by benzoin and benzene. Azoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; benzophenone, o-benzhydryl benzoic acid methyl ester, 4 -phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone a benzophenone compound such as 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloropurine Pyridone, benzyl, methyl phenylglyoxylate, titanocene compound, and the like.

Examples of the acid-forming polymerization initiator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxybenzene. Dimethyl hydrazine p-toluene sulfonate, 4-ethyl methoxy phenyl methyl benzyl hexafluoro decanoate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate And a phosphonium salt such as diphenylphosphonium p-toluenesulfonate or diphenylsulfonium hexafluoroantimonate, and nitrobenzyl methyl tosylate or benzoin tosylate.

The polymerization initiator (D) is selected from the group consisting of: O-indenyl hydrazine compound, alkyl phenone compound, three A polymerization initiator of at least one of a compound, a mercaptophosphine oxide, and a biimidazole compound is preferred, and a polymerization initiator containing an O-mercaptopurine compound is more preferred.

The total of the resin (B) and the polymerizable compound (C) The amount of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass. In the content of the polymerization initiator (D) before In the case of the above range, the sensitivity can be increased and the exposure time tends to be shortened, so that the productivity of the color filter can be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the art can be used. For example, an ester solvent (a solvent containing -COO-, a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether-ester solvent (molecular inclusion) -COO- and -O-solvent), ketone solvent (molecular-CO-, solvent free of -COO-), alcohol solvent (molecular OH, no -O-, -CO- and -COO - a solvent), an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl Anisole and the like.

Examples of the ether-ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. .

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentanone. , cyclopentanone, cyclohexanone and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 210 ° C or less is preferable in terms of coatability and drying property. In terms of solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide More preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N,N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the color hardening resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating can be improved, and the color density is not insufficient when the color filter is formed, and the display characteristics tend to be good.

<Other ingredients>

The colored curable resin composition of the present invention may contain, for example, a polymerization initiator, a leveling agent, a filler, other polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as needed. Such additives as are known in the art.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and, if necessary, It is prepared by mixing a leveling agent, a polymerization starting aid and other components.

The pigment (P) is partially or completely mixed with one of the solvent (E) in advance, and is dispersed in a bead mill or the like to preferably have an average particle diameter of about 0.2 μm or less. At this time, part or all of the pigment dispersant and the resin (B) may be blended as needed. Further, in the pigment dispersion liquid obtained in this manner, the remaining components are mixed so as to have a predetermined concentration, thereby modulating the color hardening property of the purpose. Resin composition.

The dye may be partially dissolved in a part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore diameter of about 0.01 to 1 μm.

It is preferred that the colored curable resin composition after mixing is filtered through a filter having a pore diameter of about 0.1 to 10 μm.

<Method of Manufacturing Coating Film>

The coating film of the present invention is formed from the colored curable resin composition of the present invention. This coating film can be formed by curing the colored curable resin composition. The coating film of the present invention may also contain a coloring pattern as described later. The method of hardening the colored curable resin composition will be described later.

<Method of Manufacturing Color Filter>

The color filter of the present invention is formed of the colored curable resin composition of the present invention. This color filter can be formed by hardening the colored curable resin composition. This color filter can be obtained, for example, by applying the colored curable resin composition onto a substrate, drying it to form a colored composition layer, and exposing the colored composition layer through a photomask. The color filter of the present invention may also contain a coloring pattern on the coating film.

The method of producing a colored pattern by the colored curable resin composition of the present invention may, for example, be a photolithography method, an inkjet method, a printing method, or the like. Among them, photolithography is preferred. The photo-etching method is a method in which the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and then the colored composition layer is exposed and developed through a photomask. In the photolithography method, the above can be formed by not using a photomask during exposure and/or not developing. A coating film of a cured layer of a color composition layer. The color pattern and the coating film formed in this manner are the color filters of the present invention.

The film thickness of the color filter is not particularly limited, and may be appropriately adjusted depending on the purpose, use, and the like, and is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, still more preferably 0.5 to 6 μm.

For the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, strontium oxide-coated soda lime glass, and polycarbonate, polymethyl methacrylate, and polyethylene may be used. A resin plate such as phthalate or the like, in which an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

Each color pixel is formed by photolithography, and can be carried out by conventional or conventional devices and conditions. For example, it can be produced by the following operation.

First, the colored curable resin composition is applied onto a substrate, and the volatile component such as a solvent is removed by heating (preb) and/or drying under reduced pressure, and dried to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, and a slit type spin coating method.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Moreover, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C at a pressure of from 50 to 150 Pa.

The film thickness of the colored composition layer is not particularly limited, and the color filter can be visually selected. The thickness of the device is appropriately selected.

Next, the colored composition layer is exposed through a reticle for forming a color pattern of interest. The pattern on the reticle is not particularly limited, and the pattern can be used for the purpose of the purpose.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, a filter that blocks light in a wavelength range of less than 350 nm may be used to block light in such wavelength ranges; band pass filtering of light in a wavelength range of around 436 nm, near 408 nm, and around 365 nm may also be used. , selectively extracting light of these wavelength ranges. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly illuminate the entire exposed surface with parallel rays and to align the mask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

By connecting the colored composition layer after exposure to the developer When developed by touch, a color pattern can be formed on the substrate. By developing, the unexposed portion of the colored composition layer can be removed by dissolving it in the developer. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferably used. The concentration in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Moreover, the developer may also contain a surfactant.

The development method may be any of a puddle method, a dipping method, and a spray method. Moreover, the substrate can be tilted at any angle during development.

After development, it is preferred to perform water washing.

Furthermore, the color pattern is obtained for post-baking. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

(Example)

The invention is illustrated in more detail below by the examples, but the invention is not limited by the examples. In the examples, the content and the % and the amount of the use amount are indicated, and the mass basis is not particularly limited.

In the following synthesis examples, the structure of the compound was confirmed by mass analysis (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

Example 1: Synthesis of a compound of the formula (AII-32)

To 10.9 parts of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 19 parts of triethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of acetic acid were added, and refluxed for 200 hours in 200 parts of tetrahydrofuran. After completion of the reaction, tetrahydrofuran was distilled off to obtain 29.8 parts of the compound of the formula (AII-32-1).

2.9 parts of the compound of the formula (AII-32-1) and 0.6 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-butanol and 60 parts of toluene were mixed. The resulting mixture was deionized using a Dean-Stark tube while removing 125 Stir at ° C for 3 hours. After completion of the reaction, the solvent was distilled off, and 15 parts of acetic acid was added thereto, and then 18% saline was added dropwise thereto, and the precipitated solid was collected by filtration. The filtered solid was washed with hexane. The obtained solid was dried under reduced pressure to give 3.4 parts of the compound of formula (AII-32).

Identification of compounds represented by formula (AII-32)

(mass analysis) ionization mode = ESI ⁺ : m / z = 680.4 [M + 1] ⁺

Exact Mass: 679.3

Example 2: Synthesis of a compound of the formula (AII-5)

The compound of the formula (AII-5) was obtained in the same manner as in Example 1 except that aniline was used instead of the 3-aminophenol in Example 1.

Identification of compounds represented by formula (AII-5)

(mass analysis) ionization mode = ESI ⁺ : m / z = 650.0 [M + 1] ⁺ accurate mass: 648.9

Example 3: Synthesis of a compound of the formula (AII-31)

Except that trimethoxydecane was used instead of triethoxydecane in Example 1, it was synthesized in the same manner as in Example 1 to give the formula (AII-31). Compound.

Identification of compounds represented by formula (AII-31)

(mass analysis) ionization mode = ESI ⁺ : m / z = 597.8 [M + 1] ⁺

Exact quality: 596.8

0.35 parts of the compound of the formula (AII-32), the compound of the formula (AII-5) and the compound of the formula (AII-31) are respectively dissolved in chloroform to have a volume of 250 cm ³ , and then 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g/L), and the absorption spectrum was measured with a spectrophotometer (quartz tube, light transmission distance: 1 cm). The maximum absorption wavelength of the compound: λ _max is 688 nm, 680 nm, and 687 nm, respectively.

(Measurement of solubility)

With respect to the compound obtained in Examples 1 to 3 and the compound represented by the formula (II-0), propylene glycol monomethyl ether (hereinafter abbreviated as PGME) and ethyl lactate (hereinafter, abbreviated as EL) were obtained in the following manner. The solubility of propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA).

The compound was mixed with the above solvent in a 50 mL sample tube, and then the sample tube was screwed again, and shaken in an ultrasonic oscillator at 30 ° C for 3 minutes. Then, after standing at room temperature for 30 minutes, it was suction-filtered to visually observe the residue. When the insoluble matter was not confirmed, it was judged that the solubility was good and was ○, and when the insoluble matter was confirmed, it was judged that the solubility was not Good is ×. The results are shown in Table 1.

[Synthesis of Resin]

First, an appropriate amount of nitrogen gas was introduced into a flask equipped with a circulation cooler, a dropping funnel, and a stirrer to make a nitrogen gas atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-ester and acrylic acid-3 were dissolved in 40 parts of propylene glycol monomethyl ether acetate. , a mixture of 4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-ester (containing a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel) 171 The solution was dropped into the flask using a drip pump and took about 5 hours. On the other hand, a solution of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) 26 parts dissolved in 120 parts of propylene glycol monomethyl ether acetate is used in another drop. The pump took about 5 hours to drip into the flask. After the completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content.

[Preparation of coloring curable resin composition] Example 7

The following components are mixed to obtain a colored curable resin composition:

Example 8

The following components are mixed to obtain a colored curable resin composition:

Leveling Agent (F): Polyether Modified Polyoxygenated Oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.)

0.1 parts. Example 9

The following components are mixed to obtain a colored curable resin composition:

Comparative example 2

The following components are mixed to obtain a colored curable resin composition:

[Formation of the pattern]

The colored photosensitive resin composition was applied by spin coating on a glass substrate (EAGLE XG, manufactured by CORNING Co., Ltd.), and then prebaked at 100 ° C for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the quartz glass reticle was 100 μm, and an exposure machine (TME-150RSK, manufactured by TOPCON Co., Ltd.) was used at 150 mJ/cm ² in an atmospheric gas atmosphere. The amount of exposure (base of 365 nm) illuminates the light. In the case of the mask, a pattern of 100 μm line/pitch pattern is used.

After the light was irradiated, the obtained coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for development, and after washing with water, The pattern was obtained by post-baking at 200 ° C for 20 minutes in an oven.

[Evaluation of heat resistance]

The coating film of the coloring photosensitive resin composition was heated at 200 ° C for 20 minutes, and the color difference (ΔEab*) before and after heating of the coating film was measured using a color measuring machine (OSP-SP-200, manufactured by OLYMPUS). The coating films obtained in Examples 7, 8, and 9 were each subjected to the above heat resistance evaluation, and as a result, the color difference (ΔEab*) was 12.6 (Example 7), 10.2 (Example 8), and 11.1 (Implementation) Example 9). In the same manner as in Comparative Example 2, the heat resistance was evaluated. As a result, the color difference (ΔEab*) was 20.5, and it was found that the dye of the present invention was excellent in heat resistance.

(industrial availability)

The dye of the present invention is excellent in solubility in an organic solvent. Therefore, since the colored curable resin composition of the present invention contains the dye of the present invention, the generation of foreign matter is small, and a high-quality color filter can be obtained, and a color filter excellent in heat resistance can be provided.

Claims (14)

A dye having a ruthenium-containing group and having a squarylium skeleton. The dye according to claim 1, wherein the ruthenium-containing group is a group containing -Si(R ¹⁴ ) ₃ ; and R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or a carbon number; 1 to 4 alkoxy groups; 3 R ¹⁴ groups may be the same or different. The dye according to claim 1 or 2, wherein the group containing a halogen atom is a group represented by the formula (iia); In the formula (iia), R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; and 3 R ^{14 's} may be the same or different; L ¹ represents a carbon number of 1 And alkanediyl; the -CH ₂ - contained in the alkanediyl group may also be substituted with an oxygen atom; * represents a bonding group. The dye according to claim 1 or 2, which is a compound represented by the formula (IIa); In the formula (IIa), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (constituting the saturated hydrocarbon group) An oxygen atom or a sulfur atom may be interposed between carbon atoms; R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxyl group; and R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ each independently represent hydrogen. An atom, a group containing a ruthenium atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (a carbon atom or a sulfur atom may be interposed between carbon atoms constituting the saturated carbon group) or a benzene which may have a substituent A group; at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a halogen atom. The dye according to claim 4, wherein the group containing a ruthenium atom is a group represented by the formula (iia); In the formula (iia), R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; and 3 R ^{14 's} may be the same or different; L ¹ represents a carbon number of 1 And alkanediyl; the -CH ₂ - contained in the alkanediyl group may also be substituted with an oxygen atom; * represents a bonding group. The dye according to claim 4, wherein the phenyl group which may have a substituent is a group represented by the formula (i) In the formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5; and when m is 2 or more, plural R ¹² may be the same or different; * represents a group bonded to a nitrogen atom. The dye according to claim 1 or 2, which is a compound represented by the formula (II); In the formula (II), R ^1a and R ^2a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (the carbon atoms constituting the saturated hydrocarbon group may also be inserted An oxygen atom or a sulfur atom; R ^3a and R ^4a each independently represent a hydrogen atom or a hydroxyl group; and in R ^5a and R ^6a , when one is a group represented by the formula (ii), the other is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (a carbon atom or a sulfur atom may be interposed between carbon atoms constituting the saturated hydrocarbon group) or a group represented by the formula (i); In the formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms; m represents an integer of 1 to 5; and when m is 2 or more, plural R ¹² may be the same or different; * represents a group bonded to a nitrogen atom; In the formula (ii), n represents an integer of 1 to 8; R ¹⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * represents a group bonded to a nitrogen atom. ; 3 R ¹⁴ , which can be the same or different. A coloring agent comprising the dye of claim 1, 2 or 3. The coloring agent according to item 8 of the patent application, which further contains a yellow pigment. The coloring agent according to claim 9, wherein the yellow pigment is at least one pigment selected from the group consisting of C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 150, and C.I. Pigment Yellow No. 185. A colored hardening resin composition containing the coloring agent, the resin, the polymerizable compound, and the polymerization initiator according to claim 8 or 9. A coating film formed from the color hardening resin composition described in claim 11 of the patent application. A color filter formed of the colored curable resin composition described in claim 11 of the patent application. A display device comprising the color filter of claim 13 of the patent application.