TW201840738A - Colored resin composition, color filter, and image display device capable of having excellence in contrast and light resistance - Google Patents

Abstract

The present invention provides a colored resin composition capable of forming a color filter and a display device which are excellent in contrast and light resistance. The colored resin composition according to the present invention contains a colorant and a resin, which is characterized in that: the colorant comprises an anion derived from acid-based methine dye and a divalent or higher metal cation salt. In addition, the colored resin composition according to the present invention comprises a colorant and a resin, wherein the colorant comprises a salt derived from an anion of a cyanine compound having an acid group and a divalent or higher metal cation.

Description

 Colored resin composition, color filter, and display device  

The present invention relates to a colored resin composition, a color filter, and a display device.

A color filter used in a solid-state imaging element such as a liquid crystal display device, an electroluminescence display device, a plasma display device, or the like, a solid-state imaging device such as a CCD or a CMOS sensor is manufactured from a colored resin composition. As such a coloring resin composition, a composition containing a compound represented by the formula (3) as a coloring agent is known (Patent Document 1).

Further, as the coloring agent for the colored resin composition, a compound represented by the formula (2-1) is also known.

Prior technical literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-235392

However, the color filter formed of the above-described colored resin composition known so far sometimes does not sufficiently satisfy the contrast and light resistance. Accordingly, the present invention provides a colored resin composition which can form a color filter excellent in contrast and light resistance.

The present invention includes the following inventions.

[1] A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a salt derived from an anion of a methine dye having an acid group and a metal cation having a divalent or higher value.

[2] A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a salt derived from an anion of a cyanine compound having an acid group and a metal cation having a divalent or higher value.

[3] The colored resin composition according to [1], wherein the salt is a compound represented by the formula (I).

[In the formula (I), the ring T ¹ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms or an aromatic hetero ring which may have a substituent, which has at least a substituent containing a -N(R ^a1 )(R ^a2 ) group.

The ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and which contains N or N ⁺ in a constituent atom of the ring.

L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

k represents an integer of 0 or more and 4 or less.

M ⁿ⁺ represents an n-valent metal cation.

n represents an integer of 2 or more and 5 or less.

r represents the number of Mn ⁺ , which is selected such that the valence of the formula (I) becomes zero.

R ^a1 and R ^a2 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

[4] The colored resin composition according to [3], wherein the ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ⁺ in a constituent atom of the ring, and r is 1.

[5] The colored resin composition according to any one of [1] to [4] further comprising a polymerizable compound and a polymerization initiator.

[6] A color filter formed of the colored resin composition according to any one of [1] to [5].

[7] A display device comprising the color filter according to [6].

According to the present invention, there is provided a colored resin composition which can form a color filter excellent in contrast and light resistance.

<Colored resin composition>

The coloring resin composition of the present invention contains a coloring agent (A) and a resin (B), and the coloring agent (A) includes a salt derived from an anion of a methine dye having an acid group and a metal cation having a divalent or higher value.

The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

The colored resin composition of the present invention may further comprise a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F).

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

<Colorant (A)>

The coloring resin composition of the present invention contains, as a coloring agent (A), a salt derived from an anion of a methine dye having an acid group and a metal cation of a divalent or higher, preferably containing a cyanine compound having an acid group. a salt of an anion and a metal cation of two or more valences.

The acid group is specifically a substituent capable of ionizing a hydrogen ion. As the acid group, a -COOH group or a -SO ₃ H group is preferred. The methine dye (preferably a cyanine compound) preferably has 1 to 5, more preferably 1 to 3, still more preferably 1 or 2 such acid groups.

A methine dye is a dye having at least one methine group.

A cyanine compound is a dye belonging to a multiple methyl dye, specifically means that a conjugated nitrogen atom or a C=N coloring compound is bonded to one or both ends of a methine group or a plurality of methyl chains, preferably A nitrogen atom has a + charge. As the structure of the cyanine compound, Streptocyanines, Hemicyanines or Closed chain cyanines may be used, and preferably hemi-green or closed-chain cyanine.

The methine dye having an acid group means a compound in which any hydrogen atom in the molecule constituting the methine dye is substituted with an acid group.

The cyanine compound having an acid group means a compound in which any hydrogen atom in the cyanine compound is substituted with an acid group.

In the case of a methine dye having an acid group (preferably a cyanine compound having an acid group), the hydrogen ion of the acid group is ionized to form a methine dye having an acid group (preferably having an acid group) An anion of a cyanine compound which can form a salt with a divalent or higher metal cation. The salt preferably has a valence of 0, which is electrically neutral. The metal cation having a valence of 2 or more is preferably an n-valent metal cation represented by Mn ⁺ (further, n represents an integer of 2 or more and 5 or less).

The salt derived from the anion of the methine dye having an acid group and a salt of a divalent or higher metal cation, preferably an anion derived from a cyanine compound having an acid group, and a divalent or higher metal cation are preferably A compound represented by (I) (hereinafter sometimes referred to as a compound (I)).

[In the formula (I), the ring T ¹ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms or an aromatic hetero ring which may have a substituent, which has at least a substituent containing a -N(R ^a1 )(R ^a2 ) group.

The ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and which contains N or N ⁺ in a constituent atom of the ring.

L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

k represents an integer of 0 or more and 4 or less.

M ⁿ⁺ represents an n-valent metal cation.

n represents an integer of 2 or more and 5 or less.

r represents the number of Mn ⁺ , which is selected such that the valence of the formula (I) becomes zero.

R ^a1 and R ^a2 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

Examples of the aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the ring T ¹ include aromatic monocyclic hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, and isopropyltoluene; Diene, anthracene, naphthalene, anthracene, heptene, biphenyl, asymmetry-as-indacene, symmetry-introduction, terpene, fluorene, phenalene, phenanthrene , antimony, fluoranthene, acenophene, vinegar, stilbene, hydrazine, And condensed polycyclic hydrocarbons such as tetracene. The aromatic hydrocarbon ring preferably has a carbon number of 6 to 16, more preferably 6 to 10.

The aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the ring T ¹ has at least a substituent containing a -N(R ^a1 )(R ^a2 ) group.

R ^a1 and R ^a2 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. The aliphatic hydrocarbon group having 1 to 8 carbon atoms may be any of a linear chain, a branched chain, and a cyclic group.

Examples of the linear or branched aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group; and an isopropyl group; A branched aliphatic hydrocarbon group such as an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group. The aliphatic hydrocarbon group preferably has a carbon number of from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4.

The cyclic aliphatic hydrocarbon group may be a single ring or a polycyclic ring. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The cyclic aliphatic hydrocarbon group preferably has a carbon number of from 3 to 8, more preferably from 3 to 6.

The aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the ring T ¹ may further have a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; a nitro group; a cyano group; a hydroxyl group; a methoxy group, an ethoxy group, etc. Alkoxy group having 1 to 6 carbon atoms; hydrogenthio group; alkylthio group having 1 to 6 carbon atoms such as methylthio group and ethylthio group; carboxyl group; amine carbenyl group; carbon such as methoxycarbonyl group and ethoxycarbonyl group The alkoxycarbonyl group having 1 to 6 or more; the sulfonic acid group; the amine sulfonyl group; the alkoxysulfonyl group having 1 to 6 carbon atoms such as a methoxysulfonyl group or an ethoxysulfonyl group;

The aromatic heterocyclic ring represented by the ring T ¹ contains at least one or more hetero atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as a constituent element of the ring, and the ring-forming atom has π electrons. The aromatic heterocyclic ring may be a single ring or a polycyclic ring. The aromatic heterocyclic ring preferably has a carbon number of from 3 to 30, more preferably from 3 to 20, still more preferably from 3 to 15. Examples of the aromatic heterocyclic ring represented by the ring T ¹ include an aromatic monocyclic hetero ring such as thiophene, pyrrole, furan, thiazole, oxazole, imidazole or pyrazole; anthracene, benzofluorene, benzofuran, a condensed polycyclic heterocyclic ring such as benzothiazole, benzoxazole, benzimidazole, benzopyrazole or carbazole; a hydride such as the above aromatic monocyclic hetero ring or the above fused polycyclic heterocyclic ring; The pyridone, pyrazolone or the like containing a carbonyl group in the ring also contains an aromatic heterocyclic ring. The aromatic heterocyclic ring represented by the ring T ¹ is more preferably a nitrogen atom-containing nitrogen-containing aromatic heterocyclic ring containing a nitrogen atom as a constituent element of the ring.

Examples of the nitrogen-containing aromatic heterocyclic ring in the ring T ¹ include a ring represented by the formula (T ¹ -A), the formula (T ¹ -B), and the formula (T ¹ -C).

[In the formula (T ¹ -A), the formula (T ¹ -B) and the formula (T ¹ -C), X ^1a represents -C(R ^a3 )(R ^a4 )-, -N(R ^a5 )-, - O- or -S-, preferably C(R ^a3 )(R ^a4 )-.

X ^1b is -N=C(R ^a5 )-.

R ^a3 , R ^a4 and R ^a5 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

The ring T ⁵ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.

Ia is 1 or 2.

Ib is 0, 1, or 2, preferably 0. ]

The nitrogen-containing aromatic heterocyclic ring containing N or N ⁺ in the constituent atoms of the ring represented by the ring T ² is a constituent element containing a nitrogen atom as a ring, and the nitrogen atom is -N< or >N ⁺ <, a ring-forming atom A nitrogen-containing aromatic heterocyclic ring having π electrons. The nitrogen-containing aromatic heterocyclic ring containing N or N ⁺ in the constituent atoms of the ring represented by the ring T ² preferably contains -N< or >C=N ⁺ < as a constituent element of the ring. Examples of the nitrogen-containing aromatic heterocyclic ring represented by the ring T ² include nitrogen-containing aromatic monocyclic heterocyclic rings such as pyrrole, oxazole, imidazole, and pyrazole; hydrazine, benzofluorene, benzoxazole, and benzene; A nitrogen-containing condensed polycyclic hetero ring such as imidazole, benzopyrazole or carbazole; a hydrogenated product of the above-mentioned nitrogen-containing aromatic monocyclic hetero ring, the above-mentioned nitrogen-containing condensed polycyclic hetero ring or the like. The ring T ² preferably represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and which contains N ⁺ in a constituent atom of the ring.

Examples of the nitrogen-containing aromatic heterocyclic ring in the ring T ² include a ring represented by the formula (T ² -A), the formula (T ² -B), and the formula (T ² -C).

[In the formula (T ² -A), the formula (T ² -B) and the formula (T ² -C), X ^2a represents -C(R ^a6 )(R ^a7 )-, -N(R ^a8 )-, - O- or -S-, preferably -C(R ^a6 )(R ^a7 )-.

X ^2b is -N=C(R ^a8 )-.

R ^a6 , R ^a7 and R ^a8 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

The ring T ⁶ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.

Ja is 0 or 1.

Jb is 0, 1, or 2, preferably 0. ]

The aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^a3 to R ^a8 may be any of a linear chain, a branched chain, and a cyclic group.

Examples of the linear or branched aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group; and an isopropyl group; A branched aliphatic hydrocarbon group such as an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group. The aliphatic hydrocarbon group preferably has a carbon number of from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4.

The cyclic aliphatic hydrocarbon group may be a single ring or a polycyclic ring. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The cyclic aliphatic hydrocarbon group preferably has a carbon number of from 3 to 8, more preferably from 3 to 6.

The aliphatic hydrocarbon groups having 1 to 8 carbon atoms represented by R ^a3 to R ^a8 are each independently preferably a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a carbon number. A linear alkyl group of 1 to 4 is more preferably a methyl group or an ethyl group.

Examples of the aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the rings T ⁵ and T ⁶ include aromatic monocyclic hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, and isopropyltoluene; And cyclopentadiene, anthracene, naphthalene, anthracene, heptene, biphenyl, asymmetry-inducing province, symmetry-lead province, terpene, anthracene, phenalthene, phenanthrene, anthracene, fluoranthene, vinegar Alkene, acenoate, extended triphenyl, anthracene, And condensed polycyclic hydrocarbons such as tetracene. The aromatic hydrocarbon ring preferably has a carbon number of 6 to 16, more preferably 6 to 10.

The rings T ⁵ and T ⁶ are each independently preferably benzene, naphthalene, phenalrene or anthracene, more preferably benzene or naphthalene.

Rings T ⁵ and T ⁶ may be the same or different.

An aromatic heterocyclic ring represented by the ring T ¹ , a nitrogen-containing aromatic heterocyclic ring containing N or N ⁺ in a constituent atom of the ring represented by the ring T ^{2 ,} and a carbon number 6 to 20 represented by the rings T ⁵ and T ⁶ The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include a pendant oxy group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; a nitro group; a cyano group; and a -N(R ^a1 )(R ^a2 ) group (wherein R ^{a1 )} And R ^a2 are the same as above; a hydroxyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydrogenthio group; an alkylthio group having 1 to 6 carbon atoms such as a methylthio group or an ethylthio group; Alkoxycarbonyl group having a carbon number of 1 to 6 such as a methoxycarbonyl group or an ethoxycarbonyl group; a sulfonic acid group; an aminesulfonyl group; a methoxysulfonyl group, an ethoxysulfonyl group; And other alkoxysulfonyl groups having 1 to 6 carbon atoms.

Of formula (I), ring T ¹ is a hydrogen atom in any ring T ¹ contained in the portion out of the two binding carbon atoms, L ¹ and, in the cycle T ² of the cycle T ² contained in arbitrary hydrogen atom The two parts are separated from L ² and carbon atoms.

Rings T ¹ and T ² may be the same or different.

The divalent hydrocarbon group having 1 to 8 carbon atoms represented by L ¹ and L ² is a divalent group derived by removing two arbitrary hydrogen atoms from a hydrocarbon having 1 to 8 carbon atoms, and examples thereof include A divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

Examples of the divalent aliphatic hydrocarbon group include a divalent chain hydrocarbon group having 1 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.

The divalent chain aliphatic hydrocarbon group may, for example, be a methyl group, an ethyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

Examples of the divalent alicyclic hydrocarbon group include a cyclopropane-1,1-diyl group, a cyclopropane-1,2-diyl group, a cyclobutane-1,1-diyl group, and a cyclobutane-1,2. -diyl, cyclobutane-1,3-diyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexyl Alkan-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl and from formula (L-a1)~ A group represented by the formula (L-a6) or the like.

The divalent aromatic hydrocarbon group having 6 to 8 carbon atoms is preferably a divalent aromatic monocyclic hydrocarbon group having 6 to 8 carbon atoms, and the divalent aromatic monocyclic hydrocarbon group is an o-phenylene group. , m-phenylene, p-phenylene, and a group represented by the formula (L-b1) to the formula (L-b6).

The divalent hydrocarbon group having 1 to 8 carbon atoms represented by L ¹ and L ² is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms, more preferably a divalent chain hydrocarbon group having 1 to 8 carbon atoms or a divalent aromatic monocyclic hydrocarbon group having 6 to 8 carbon atoms, more preferably a C 1-8 alkyl group or a C 6 to 7 carbon number The aromatic monocyclic hydrocarbon group is particularly preferably a linear alkyl group having 1 to 8 carbon atoms or a divalent aromatic monocyclic hydrocarbon group having 6 carbon atoms.

Further, the carbon number of the divalent aliphatic hydrocarbon group is preferably from 1 to 6, more preferably from 1 to 4.

The divalent hydrocarbon group having 1 to 8 carbon atoms in L ¹ and L ² may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; a nitro group; Amino group; hydroxyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; hydrogenthio group; alkylthio group having 1 to 6 carbon atoms such as methylthio group and ethylthio group; carboxyl group; Mercapto group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; sulfonic acid group; amine sulfonyl group; methoxy sulfonyl group, ethoxy sulfonyl group and the like ~6 alkoxysulfonyl group and the like.

The divalent hydrocarbon group preferably does not have a substituent.

L ¹ and L ² are each independently preferably a methyl group, an ethyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a formula (L-b1)~(L- a group represented by b6), o-phenylene, m-phenylene or p-phenylene, more preferably methyl, ethyl, propane-1,3-diyl, butane-1, 4-diyl, o-phenylene, m-phenyl or p-phenyl. Further, L ¹ and L ² may be the same or different, but preferably both are the same.

k is preferably 3 or less, more preferably 2 or less. Further, in the formula (I), the carbon-carbon double bond represented by the arrows s and t may be either an E configuration or a Z configuration. That is, the formula (I) is defined as all geometric isomers including the carbon-carbon double bond represented by the arrows s and t, and is also the same in the formula (II), the formula (III-A) and the formula (III-B). .

Examples of the n-valent metal ion represented by Mn ⁺ include alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and strontium ions; titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, and cobalt ions. Transition metal ions such as nickel ions and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and cesium ions.

n is preferably 4 or less, more preferably 3 or less, still more preferably 2.

Since the valence of the compound (I) is 0, that is, an electrically neutral compound, the number r of Mn ⁺ is selected so that the valence of the compound (I) becomes zero. r is preferably 1 or 2, more preferably 1.

M ^{n+ is more} preferably an alkaline earth metal ion or a typical metal ion, and more preferably a magnesium ion, a barium ion or an aluminum ion, and more preferably a barium ion or an aluminum ion.

The compound (I) is preferably a compound represented by the formula (II) (hereinafter sometimes referred to as a compound (II)).

[In the formula (II), L ¹ , L ² , k, r, M ⁿ⁺ and n are the same as described above.

Ring T ³ represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent.

The ring T ⁴ represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N or N ⁺ in a constituent atom of the ring.

L ³ represents a single bond or -CO-.

L ⁴ represents a double bond or -CO-. ]

The nitrogen-containing aromatic heterocyclic ring represented by the ring T ³ is a nitrogen-containing aromatic heterocyclic ring containing a nitrogen atom as a ring, the nitrogen atom is a nitrogen-containing aromatic heterocyclic ring of >N-, and the ring-forming atom has a π-electron as a ring T ³ . A ring represented by the formula (T ³ -A), the formula (T ³ -B), the formula (T ³ -C) or the formula (T ³ -D).

The nitrogen-containing aromatic heterocyclic ring containing N or N ⁺ in the constituent atoms of the ring represented by the ring T ⁴ is a constituent element containing a nitrogen atom as a ring, and the nitrogen atom is -N< or >N ⁺ <, a ring forming atom a nitrogen-containing aromatic heterocyclic ring having π electrons, as the ring T ⁴ , preferably of the formula (T ⁴ -A), the formula (T ⁴ -B), the formula (T ⁴ -C) or the formula (T ⁴ -D) The ring represented.

Rings T ³ and T ⁴ may be the same or different.

[Formula (T ³ -A), Formula (T ³ -B), Formula (T ³ -C), Formula (T ³ -D), Formula (T ⁴ -A), Formula (T ⁴ -B), Formula In (T ⁴ -C) and the formula (T ⁴ -D), X ^1a , X ^2a , X ^1b , X ^2b , ring T ⁵ and ring T ⁶ are the same as described above. *L means a bonding end with L ¹ or L ² , and *C means a bonding end with a carbon atom. ]

The ring T ¹ and the ring T ^{3 are more} preferably a ring represented by the formula (R ³ -1) to the formula (R ³ -7), and more preferably a formula (R ³ -1) to the formula (R ³ -3). A ring represented by the formula (R ³ -7). The ring T ² and the ring T ^{4 are more} preferably a ring represented by the formula (R ⁴ -1) to the formula (R ⁴ -7), and more preferably a formula (R ⁴ -1)~ (R ⁴ -3) A ring represented by the formula (R ⁴ -7).

The compound (I) and the compound (II) are more preferably a compound represented by the formula (III-A) (hereinafter sometimes referred to as a compound (III-A)) or a compound represented by the formula (III-B) (hereinafter sometimes It is called compound (III-B)).

[In the formula (III-A), the ring T ⁵ , the ring T ⁶ , L ¹ , L ² , k, r, M ⁿ⁺ and n are the same as described above. ]

[In the formula (III-B), L ¹ , L ² , k, r, M ⁿ⁺ and n are the same as described above. ]

Examples of the compound (I) include compounds represented by the formula (I-1) to the formula (I-189) shown in Tables 1 to 3. The compound (I) is preferably a compound represented by the formula (I-1) to the formula (I-63), and the formula (I-127) to the formula (I-168), more preferably from the formula (I-43). The compound represented by the formula (I-63), the formula (I-127) to the formula (I-133), the formula (I-148) to the formula (I-154), and more preferably the formula (I-43)~ A compound represented by the formula (I-54), the formula (I-131) to the formula (I-133), and the formula (I-152) to the formula (I-154).

In Tables 1 to 3, the ring T ¹ represents a ring represented by the formula (R ^{3 -} a1) to the formula (R ^{3 -} a4), and the ring T ² represents a formula (R ^{4 -} a1) - (R ^{4 -} a4) The ring represented. In the formula (R ^{3 -} a1) to the formula (R ^{3 -} a4) and the formula (R ^{4 -} a1) to the formula (R ^{4 -} a4), *L and *C are the same as described above.

In Tables 1 to 3, L ¹ and L ² represent a divalent hydrocarbon group represented by the formula (L-1) to the formula (L-7). In the formula (L-1) to the formula (L-7), *n means a bonding end with a nitrogen atom, and *s means a bonding end with a sulfur atom.

Further, the compound represented by the formula (I) can be obtained by a compound represented by the formula (pt3) and a halide (preferably chloride) containing an n-valent metal ion, a hydroxide, an acetate, a phosphate, It is produced by reacting a sulfate, a citrate or a cyanide.

Further, a compound represented by the formula (pt3), wherein L ¹ is the same as L ² and >N-CH< of the ring T ¹ and the ring T ² in each ring The moiety other than >N ⁺ =C< is the same, and can be produced by reacting the compound represented by the formula (pt1) with the compound represented by the formula (pt2) under acidic or basic conditions. In the present reaction, the compound represented by the formula (pt1) is preferably used in an amount of from 1.5 to 2.5 mol per mol of the compound 1 represented by the formula (pt2).

[In the formula (pt2), R ^c is a hydrogen atom, a nitro group or a halogen atom; k is the same as above. In the formula (pt1), the formula (pt3), and the formula (I), the ring T ¹ , the ring T ² , L ¹ , L ² , k, M ⁿ⁺ and n are the same as described above. ]

The content of the compound (I) is preferably from 0.1 to 150 parts by weight, more preferably from 1 to 100 parts by weight, still more preferably from 5 to 80 parts by weight, per 100 parts by weight of the resin (B).

In the colored resin composition of the present invention, the colorant (A) may contain the dye (A1) and the pigment (A2) in addition to the compound (I).

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mord dyes. Examples of the dye include a compound having a color tone other than a pigment in a color index (published by The Society of Dyers and Colourists), and a known dye described in a dyeing note (color dyeing company). In addition, examples of the chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, and methine dyes. Azomethine dyes, squaric acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and a known pigment can be used. For example, a pigment classified as a pigment in the excellent index (published by The Society of Dyers and Colourists) can be cited.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, and 125. Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, Red pigments such as 224, 242, 254, 255, 264, 265; Cyan blue 15, 15:3, 15:4, 15:6, 60 and other cyan pigments; CI pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

The content of the colorant (A) is preferably from 0.1 to 70% by weight, more preferably from 0.5 to 60% by weight, still more preferably from 1 to 50% by weight, based on the total amount of the solid components.

The content of the compound (I) in the total amount of the colorant (A) is preferably 50% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more.

Here, the "total amount of solid content" in the present specification means an amount after the content of the solvent is removed from the total amount of the colored resin composition. The total amount of the solid components and the content of each component with respect to the solid components can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a) ") Resin of the structural unit. Further, the resin (B) is more preferably a structural unit having at least one selected from the group consisting of a monomer having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (b) (hereinafter sometimes referred to as The structural unit of "(b)") is derived from a monomer (c) copolymerizable with (a) (hereinafter sometimes referred to as "(c)", but different from (a) and (b)) A structural unit and a structural unit having an ethylenically unsaturated bond in a side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, isaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono [2-(A). The acryloyloxyethyl]ester or the like is preferably acrylic acid, methacrylic acid or maleic anhydride.

(b) preferably having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloxy group Monomer.

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)acrylinyl" and "(meth)acrylate" have the same meaning.

Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate. , 3-ethyl-3-(methyl)propenyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (methyl) 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate, 3-ethyl-3-(methyl)propenyloxymethyloxetane.

Examples of (c) include methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and (methyl). ) Tricycloacrylic acid [5.2.1.0 ^2,6 ]decane-8-yl ester, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N - cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyl toluene, etc., preferably styrene, vinyl toluene, 2-hydroxyethyl (meth)acrylate, N-benzene Kimalyimide, N-cyclohexylmaleimide, N-benzylmaleimide, and the like.

A resin having a structural unit having an ethylenically unsaturated bond in a side chain can be obtained by adding (b) to the copolymer of (a) and (c) or (a) to (b) and (c) Manufactured from a copolymer. The resin may be a resin obtained by adding (a) a copolymer of (b) to (c) and further reacting with a carboxylic anhydride.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000.

The degree of dispersion (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 20 to 170 mg-KOH/g, more preferably from 30 to 150 mg-KOH/g, still more preferably from 40 to 135 mg-KOH/g, in terms of solid content. In addition, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65% by weight, more preferably from 13 to 60% by weight, still more preferably from 17 to 55% by weight, based on the total amount of the solid components.

The colored resin composition of the present invention may contain a polymerizable compound (C) and a polymerization initiator (D). Hereinafter, the colored resin composition containing the polymerizable compound (C) and the polymerization initiator (D) may be referred to as a "colored curable resin composition".

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by using an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. (Meth) acrylate compound.

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 penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, and the like.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably from 7 to 65% by weight, more preferably from 13 to 60% by weight, still more preferably 17% based on the total amount of the solid component. ~55% by weight.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound which generates an active radical, an acid or the like by polymerization of light or heat, and can initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator which generates the living radicals include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine and N-benzamide. Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-one-2-imine, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-mallowyl-1,3 , 5-triazine, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four Phenylbiimidazole and the like.

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight based on 100 parts by total of the total of the resin (B) and the polymerizable compound (C). It is 1 to 20 parts by weight. When the content of the polymerization initiator (D) is within the above range, the sensitivity is high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

The coloring resin composition of the present invention may contain a polymerization initiation aid (D1).

<Polymerization Initiator (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable polymerizable compound by a polymerization initiator. In the case where the polymerization initiation aid (D1) is contained, the polymerization initiation aid (D1) is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler) and 4,4'-bis(diethylamino)di. Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, and the like.

When the polymerization initiation aid (D1) is used, the content thereof is preferably from 0.1 to 30 parts by weight, more preferably from 1 to 20, based on 100 parts by weight of the total of the resin (B) and the polymerizable compound (C). Parts by weight. If the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be further formed with high sensitivity, and the productivity of the color filter can be improved.

The colored resin composition of the present invention may contain a solvent (E).

<Solvent (E)>

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

Examples of the solvent include ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, and methyl acetate. An ester solvent such as cyclohexanol acetate and γ-butyrolactone (a solvent containing -COO- in the molecule and containing no -O-); ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, An ether solvent such as propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether or diethylene glycol methyl ethyl ether (containing -O- in the molecule and not containing - Solvent for COO-); methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether ester solvent such as ether acetate or diethylene glycol monoethyl ether acetate (solvent containing -COO- and -O- in the molecule); 4-hydroxy-4-methyl-2-pentanone, a ketone solvent such as heptanone, 4-methyl-2-pentanone or cyclohexanone (a solvent containing -CO- in the molecule and containing no -COO-); an alcohol solvent such as butanol, cyclohexanol or propylene glycol (at a solvent containing OH in the molecule and containing no -O-, -CO- and -COO-; N,N-dimethylformamide, N,N-dimethylacetamide and N- A guanamine solvent such as methylpyrrolidone or the like.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

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

The coloring resin composition of the present invention may comprise a leveling agent (F).

<Leveling agent (F)>

Examples of the leveling agent (F) include an organic lanthanoid surfactant, a fluorine-based surfactant, and an organic lanthanoid surfactant having a fluorine atom. They may have a polymerizable group in the side chain.

Examples of the organic oxime-based surfactant include surfactants having a decane bond in the molecule. Specific examples thereof include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade name: manufactured by Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 ( Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by Momentive Advanced Materials Japan Co., Ltd.).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, FLUORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), MEGAFAC (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K ( DIC (manufactured by Asahi Glass Co., Ltd.), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Integrated Materials Electronic Chemicals Co., Ltd.), SURFLON (registered trademark) S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) And E5844 (manufactured by Daikin Fine Chemical Research Institute).

The organic ruthenium-based surfactant having a fluorine atom as described above includes a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC) can be cited.

In the case where the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2% by weight, more preferably 0.002 to 0.1% by weight based on the total amount of the colored resin composition. Incidentally, the content of the pigment dispersant is not contained in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored resin composition of the present invention may contain additives known in the art such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as needed.

<Method for Producing Colored Resin Composition>

The coloring resin composition of the present invention can be obtained by using a coloring agent (A) and a resin (B), and a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation aid (D1), and a solvent, which are used as needed. (E), leveling agent (F) and other ingredients are prepared by mixing.

<Method of Manufacturing Color Filter>

Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred.

By including the compound (I) as a colorant in the colored resin composition, it is possible to produce a color filter which is particularly excellent in contrast and light resistance. The color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic electroluminescence devices, electronic paper, etc.) and solid-state imaging elements.

Example

The colored resin composition of the present invention will be described in more detail below by way of examples. The "%" and "parts" in the examples are % by weight and parts by weight unless otherwise specified.

Example 1

9.2 parts of the compound represented by the formula (1-1) and 5.5 parts of the compound represented by the formula (1-2) were added to 18 parts of acetic anhydride, and they were mixed at room temperature. Next, after adding 8 parts of triethylamine, it stirred for 5 hours at 40 degreeC. After completion of the reaction, 100 parts of ethyl acetate was added to precipitate crystals, followed by filtration. The mixture was washed three times with 80 parts of ethyl acetate, and the crystals were dried under reduced pressure at 60 ° C to obtain 8.4 parts of the compound of formula (1-3).

11 parts of the compound represented by the formula (1-3) was added to 100 parts of water to prepare a liquid (aqueous solution 1) in which the compound represented by the formula (1-3) was dissolved. Separately, a liquid (aqueous solution 2) in which 19.5 parts of cerium chloride dihydrate was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was dropped into the aqueous solution 1 at 40 ° C over 2 hours, and then stirred for 4 hours. After cooling, it was filtered, washed twice with 100 parts of ion-exchanged water, and the crystals were dried under reduced pressure at 100 ° C to obtain 18 parts of the compound represented by the formula (I-52).

Example 2

5.2 parts of the compound represented by the formula (2-1) was added to 100 parts of water to prepare a liquid (aqueous solution 1) in which the compound represented by the formula (2-1) was dissolved. Separately, a liquid (aqueous solution 2) in which 7.1 parts of aluminum hydroxide was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was dropped into the aqueous solution 1 at 40 ° C over 2 hours, and then stirred for 4 hours. After cooling, the mixture was filtered and washed twice with 100 parts of ion-exchanged water, and the crystals were dried under reduced pressure at 100 ° C to obtain 1.8 parts of a compound represented by formula (I-152).

Example 3

5.2 parts of the compound represented by the formula (2-1) was added to 100 parts of water to prepare a liquid (aqueous solution 1) in which the compound represented by the formula (2-1) was dissolved. Separately, a liquid (aqueous solution 2) in which 12.2 parts of cerium chloride dihydrate was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was dropped into the aqueous solution 1 at 40 ° C over 2 hours, and then stirred for 4 hours. After cooling, the mixture was filtered and washed twice with 100 parts of ion-exchanged water, and the crystals were dried under reduced pressure at 100 ° C to obtain 5.9 parts of the compound represented by formula (I-131).

[Synthesis Example 1]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80 ° C while stirring. Next, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and acrylic acid were dropped using a drip pump for about 5 hours. a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester (trade name "E-DCPA", manufactured by Daicel), 289 parts dissolved in propylene glycol monomethyl ether A solution of 125 parts of acetate. On the other hand, 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate using an additional drip pump for about 6 hours. The solution in the solution was dropped into the flask. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The obtained copolymer had a weight average molecular weight Mw of 9,200, a degree of dispersion of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content. The resin (B-2) has the following structural unit.

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out by gel permeation chromatography (GPC method) under the following conditions.

Device: HLC-8120GPC (made by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Solid concentration of the tested liquid: 0.001~0.01% by weight

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

Example 4

[Production of Dispersion (P-1)]

10 parts of the compound represented by the formula (I-52), 4 parts of a solid component of a dispersing agent BYK-LP N6919 (manufactured by BYK), and 5 parts of a resin (B-2) solution (solid content: 35.0%) (based on solid content) After weighing 181 parts of propylene glycol monomethyl ether acetate, 300 parts of 0.4 μm zirconia beads were placed, and shaken for 6 hours using a paint conditioner (manufactured by LAU Co., Ltd.) to remove zirconia beads by filtration. A dispersion (P-1) was prepared.

[Preparation of Colored Resin Composition]

The components were mixed so as to have the composition shown in Table 4, and a colored resin composition was obtained.

Comparative example 1

A colored resin composition was obtained in the same manner as in Example 4 except that the dispersion (P-1) was changed to the colorant (A-1).

In Table 4, each component represents the following compound.

Colorant (A-1): a compound represented by formula (3)

Resin (B-2): Resin (B-2) (converted in solid content)

Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D-1): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation Manufacturing)

Solvent (E-1): propylene glycol monomethyl ether acetate

Example 5

[Production of Dispersion (P-2)]

In the same manner as in Example 4 except that the compound represented by the formula (I-52) was changed to the compound represented by the formula (I-152), a dispersion (P-2) was produced.

[Preparation of Colored Resin Composition]

The components were mixed so as to have the composition shown in Table 5, and a colored resin composition was obtained.

Example 6

[Production of Dispersion (P-3)]

In the same manner as in Example 4 except that the compound represented by the formula (I-52) was changed to the compound represented by the formula (I-131), a dispersion liquid (P-3) was produced.

[Preparation of Colored Resin Composition]

The components were mixed so as to have the composition shown in Table 5, and a colored resin composition was obtained.

Comparative example 2

A colored resin composition was obtained in the same manner as in Example 5 except that the dispersion (P-1) was changed to the colorant (2-1).

In Table 5, each component represents the following compound.

Colorant (2-1): a compound represented by formula (2-1)

Resin (B-2): Resin (B-2) (converted in solid content)

Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D-1): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation Manufacturing)

Solvent (E-1): propylene glycol monomethyl ether acetate

<Production of coloring pattern>

The colored resin composition was applied onto a 5 cm ² glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon) was used at 150 mJ/cm in an air atmosphere. The exposure amount of ² (365 nm reference) was irradiated with light. The reticle has a 100 [mu]m line and gap pattern. The colored composition layer after light irradiation was immersed and developed at 24 ° C for 60 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then dried in an oven at 200 ° C. Baking for 20 minutes gave a colored pattern.

<Contrast evaluation>

For the coloring patterns obtained in Example 4 and Comparative Example 1, a contrast meter (CT-1: manufactured by Kesaka Electric Co., Ltd., color difference meter BM-5A: manufactured by Topcon Co., Ltd., light source: F-10, was used. Polarized film: manufactured by Kesaka Electric Co., Ltd.), the blank value was set to 30,000, and the contrast was measured. The results are shown in Table 6.

<Light resistance evaluation>

An ultraviolet cut-off filter (COLORED OPTICAL GLASS L38; manufactured by HOYA Co., Ltd.; cut light of 380 nm or less) was placed on the obtained coloring pattern, and the light was irradiated with a light resistance tester (SUNTEST CPS+: manufactured by Toyo Seiki Co., Ltd.). The chromaticity of the colored pattern after the irradiation was measured for 48 hours, and the color difference (ΔEab*) before and after the irradiation was obtained from the measured value by the method described in JIS Z 8730:2009 (7. Method for calculating the color difference). Further, in terms of chromaticity, the color measurement was measured using a color measuring machine (OSP-SP-200: manufactured by Olympus), and the xy in the XYZ color system of CIE was measured using the isochromatic function of the C light source. Chromaticity coordinates (x, y) and stimulus values Y. The results are shown in Table 7.

Industrial availability

According to the colored resin composition of the present invention, a color filter excellent in contrast and light resistance can be produced.

Claims (7)

 A colored resin composition comprising a colorant and a resin, the colorant comprising: an anion derived from a methine dye having an acid group and a salt of a divalent or higher metal cation.    A colored resin composition comprising a colorant and a resin, the colorant comprising: an anion derived from a cyanine compound having an acid group and a salt of a divalent or higher metal cation.   The colored resin composition according to claim 1 or 2, wherein the salt is a compound represented by the formula (I), In the formula (I), the ring T ¹ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms or a heterocyclic ring which may have a substituent, which has at least a substituent containing a -N(R ^a1 )(R ^a2 ) group, and a ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N or N ⁺ in a constituent atom of the ring, and L ¹ and L ² each independently represent a divalent valence of 1 to 8 carbon atoms which may have a substituent. The hydrocarbon group, k represents an integer of 0 or more and 4 or less, M ⁿ⁺ represents an n-valent metal cation, n represents an integer of 2 or more and 5 or less, and r represents the number of Mn ⁺ , which is selected such that the formula (I) The valence is 0, and R ^a1 and R ^a2 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. The colored resin composition according to claim 3, wherein the ring T ² represents a nitrogen-containing aromatic heterocyclic ring which may have a substituent and contains N ⁺ in a constituent atom of the ring, and r is 1.  The colored resin composition according to any one of claims 1 to 4, further comprising a polymerizable compound and a polymerization initiator.    A color filter formed of the colored resin composition according to any one of claims 1 to 5.    A display device comprising the color filter according to claim 6.