JP6931620B2 - Colored resin composition - Google Patents

Description

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

Color filters used in display devices such as liquid crystal displays, electroluminescence display devices and plasma displays, and solid-state image sensors such as CCDs and CMOS sensors are manufactured from colored resin compositions. As such a colored resin composition, a composition containing a compound represented by the formula (3) as a colorant is known (Patent Document 1).

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

JP-A-2009-235392

However, the color filter formed from the above-mentioned colored resin composition known conventionally may not sufficiently satisfy the contrast and light resistance. Therefore, the present invention provides a colored resin composition capable of forming a color filter having excellent contrast and light resistance.

［式（Ｉ）中、
環Ｔ^１は、少なくとも−Ｎ（Ｒ^ａ１）（Ｒ^ａ２）基を含む置換基を有する炭素数６〜２０の芳香族炭化水素環または置換基を有していてもよい芳香族複素環を表す。
環Ｔ^２は、置換基を有していてもよい環の構成原子にＮまたはＮ^＋を含む含窒素芳香族複素環を表す。
Ｌ^１及びＬ^２は、それぞれ独立に、置換基を有していてもよい炭素数１〜８の２価の炭化水素基を表す。
ｋは、０以上４以下の整数を表す。
Ｍ^ｎ＋は、ｎ価の金属カチオンを表す。
ｎは、２以上５以下の整数を表す。
ｒは、Ｍ^ｎ＋の個数を表し、式（Ｉ）の価数が０となるように選択される。
Ｒ^ａ１及びＲ^ａ２は、それぞれ独立に、水素原子または炭素数１〜８の脂肪族炭化水素基を表す。］
［４］ 前記環Ｔ^２は、置換基を有していてもよい環の構成原子にＮ^＋を含む含窒素芳香族複素環を表し、ｒが１である［３］に記載の着色樹脂組成物。
［５］ さらに、重合性化合物及び重合開始剤を含む［１］〜［４］のいずれか記載の着色樹脂組成物。
［６］ ［１］〜［５］のいずれか記載の着色樹脂組成物から形成されるカラーフィルタ。
［７］ ［６］記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A colored resin composition containing a colorant and a resin, wherein the colorant contains a salt of an anion derived from a methine dye having an acid group and a metal cation having a divalent value or higher.
[2] A colored resin composition containing a colorant and a resin, wherein the colorant contains a salt of an anion derived from a cyanine compound having an acid group and a metal cation having a divalent value or higher.
[3] The colored resin composition according to [1] or [2], wherein the salt is a compound represented by the formula (I).

[In formula (I),
Ring T ¹ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms having a substituent containing at least -N ( ^Ra1 ) ( ^{Ra2) group or an aromatic heterocycle which may have a substituent.} ..
Ring T ² represents a nitrogen-containing aromatic heterocycle containing ^{N or N +} as a constituent atom of the ring which may have a substituent.
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 M n +} and is selected so that the valence of the formula (I) is 0.
R ^a1 and R ^a2 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 heterocycle containing N +} as a constituent atom of the ring which may have a substituent, and r is 1. thing.
[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 from the colored resin composition according to any one of [1] to [5].
[7] A display device including the color filter according to [6].

According to the present invention, there is provided a colored resin composition capable of forming a color filter having excellent contrast and light resistance.

<Colored resin composition>
The colored resin composition of the present invention contains a colorant (A) and a resin (B), and as the colorant (A), a salt of an anion derived from a methine dye having an acid group and a divalent or higher valent metal cation is used. include.
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 contain a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F).
In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

<Colorant (A)>
The colored resin composition of the present invention contains, as the colorant (A), a salt of an anion derived from a methine dye having an acid group and a metal cation having a divalent value or higher, preferably an anion derived from a cyanine compound having an acid group. Contains salts with divalent or higher metal cations.

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

A methine dye is a dye having at least one methine group.
The cyanine compound is a dye belonging to a polymethine dye, and specifically means a colored compound in which a nitrogen atom or C = N bonded to one end or both ends of a methine group or a polymethine chain is bonded, and one nitrogen atom is used. Most preferably, it has a + charge. The structure of the cyanine compound may be either Streptocyanines, Hemicyanines or Closed chain cyanines, preferably Hemicyanines or Closed chain cyanines.
The methine dye having an acid group is a compound in which an arbitrary hydrogen atom in a molecule constituting the methine dye is replaced with an acid group.
The cyanine compound having an acid group means a compound in which an arbitrary hydrogen atom in the cyanine compound is substituted with an acid group.

The methine dye having an acid group (preferably a cyanine compound having an acid group) has an anion derived from the methine dye having an acid group (preferably a cyanine compound having an acid group) by ionizing the hydrogen ion of the acid group. Once formed, the anion can form a salt with a divalent or higher valent metal cation. The salt preferably has a valence of 0, i.e., is electrically neutral. As the divalent or higher valent metal cation, ^{an n-valent metal cation represented by M n +} (where n represents an integer of 2 or more and 5 or less) is preferable.

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

[In formula (I),
Ring T ¹ represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms having a substituent containing at least -N ( ^Ra1 ) ( ^{Ra2) group or an aromatic heterocycle which may have a substituent.} ..
Ring T ² represents a nitrogen-containing aromatic heterocycle containing ^{N or N +} as a constituent atom of the ring which may have a substituent.
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 M n +} and is selected so that the valence of the formula (I) is 0.
R ^a1 and R ^a2 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 ring T ¹ include aromatic monocyclic hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, and simen; pentalene, inden, naphthalene, azulene, and heptalene. , Biphenylene, as-indacene, s-indacene, acenaphthalene, fluorene, phenalene, phenanthrene, anthracene, fluorantene, acephenanthrene, acetylene, triphenylene, pyrene, chrysene, tetracene and other condensed polycyclic hydrocarbons; Be done. The aromatic hydrocarbon ring has preferably 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms.

Aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the ring ^{T 1} has a substituent containing at least ^{-N (R a1) (R a2} ) group.
R ^a1 and R ^a2 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 linear, branched or cyclic.
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 and an octyl group; Examples thereof include branched chain aliphatic hydrocarbon groups such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group. The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 4 carbon atoms.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. The cyclic aliphatic hydrocarbon group preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.
Aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by the ring T ¹ is further fluorine atom, a chlorine atom, an iodine atom, a halogen atom such as a bromine atom; a nitro group; a cyano group; a hydroxyl group; methoxy group, An alkoxy group having 1 to 6 carbon atoms such as an ethoxy group; a sulfanyl group; an alkylsulfanyl group having 1 to 6 carbon atoms such as a methylsulfanyl group and an ethylsulfanyl group; a carboxy group; a carbamoyl group; a methoxycarbonyl group, an ethoxycarbonyl group and the like. An alkoxycarbonyl group having 1 to 6 carbon atoms; a sulfo group; a sulfamoyl group; an alkoxysulfonyl group having 1 to 6 carbon atoms such as a methoxysulfonyl group and an ethoxysulfonyl group; and the like may be used as a substituent.

The aromatic heterocycle represented by ring T ¹ contains at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom as a ring component, and the ring-forming atom has π electrons. .. The aromatic heterocycle may be monocyclic or polycyclic. The aromatic heterocycle preferably has 3 to 30, more preferably 3 to 20, and even more preferably 3 to 15. Examples of the ^{aromatic heterocycle represented by ring T 1} include aromatic monocyclic heterocycles such as thiophene, pyrrole, furan, thiazole, oxazole, imidazole, and pyrazole; indole, benzoindole, benzofuran, benzothiazole, benzoxazole, and benzo. Condensed polycyclic heterocycles such as imidazole, benzopyrazole, and carbazole; hydrides such as the aromatic monocyclic heterocycle and the condensed polycyclic heterocycle; and the like, and pyridone, pyrazolone, etc. containing a carbonyl group in the ring are also aromatic. Included in the group heterocycle. The aromatic heterocycle represented by ring T ¹ is more preferably a nitrogen-containing aromatic heterocycle containing a nitrogen atom as a component of the ring and having a nitrogen atom of> N−.

Examples of the nitrogen-containing aromatic heterocyclic ring in ring ^{T 1,} formula ^(T 1 -A), formula ^(T 1 -B), and ring, and the like represented by 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 ( ^Ra5 ) −.
R ^a3 , R ^a4 and R ^a5 each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a hydrogen atom or a substituent.
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. ]

^{A nitrogen-containing aromatic heterocycle containing N or N +} in the constituent atoms of the ring represented by ring T ² is a nitrogen-containing aromatic heterocycle containing a nitrogen atom as a constituent element of the ring, and the nitrogen atom is −N <or> N ⁺ <. It is a nitrogen-containing aromatic heterocycle in which the ring-forming atom has π electrons. ^{The nitrogen-containing aromatic heterocycle containing N or N +} as a constituent atom of the ring represented by ring T ² more preferably contains −N <or> C = N ^{+ <as a component of the ring.} Examples of the nitrogen-containing aromatic heterocycle represented by ring T ² include nitrogen-containing aromatic monocyclic heterocycles such as pyrazole, oxazole, imidazole, and pyrazole; indol, benzoindole, benzoxazole, benzoimidazole, benzopyrazole, carbazole, and the like. Nitrogen-containing condensed polycyclic heterocycles; hydrides such as the nitrogen-containing aromatic monocyclic heterocycle and the nitrogen-containing condensed polycyclic heterocycle; and the like. Ring T ² preferably represents a nitrogen-containing aromatic heterocycle containing ^{N +} as a constituent atom of the ring, which may have a substituent.

Examples of the nitrogen-containing aromatic heterocyclic ring in ring ^{T 2,} the formula ^(T 2 -A), formula ^(T 2 -B), and ring, and the like represented by the formula ^(T 2 -C).

Expression ^(T 2 -A), formula ^(T 2 -B), and wherein ^(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 ( ^Ra8 ) −.
R ^a6 , R ^a7 and R ^a8 each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a hydrogen atom or a substituent.
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 linear, branched or cyclic.}
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 and an octyl group; Examples thereof include branched chain aliphatic hydrocarbon groups such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group. The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 4 carbon atoms.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. The cyclic aliphatic hydrocarbon group preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.
The aliphatic hydrocarbon groups having 1 to 8 carbon atoms represented by R ^{a3 to} R ^a8 are preferably hydrogen atoms or linear or branched aliphatic hydrocarbon groups having 1 to 6 carbon atoms, respectively. , A hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.

The aromatic hydrocarbon ring having 6 to 20 carbon atoms represented by ring T ⁵ and T ^6, benzene, toluene, xylene, mesitylene, cumene, aromatic monocyclic hydrocarbon of cymene and the like; pentalene, indene, naphthalene, Condensed polycyclic hydrocarbons such as azulene, heptalene, biphenylene, as-indacene, s-indacene, acenaphthalene, fluorene, phenalene, phenanthrene, anthracene, fluorantene, acephenanthrene, aceanthrylene, triphenylene, pyrene, chrycene, tetracene; And so on. The aromatic hydrocarbon ring has preferably 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms.
Rings T ⁵ and T ⁶ are independently, preferably benzene, naphthalene, phenalene or anthracene, more preferably benzene or naphthalene, respectively.
Rings T ⁵ and T ⁶ may be the same or different.

An aromatic heterocycle represented by ring T ¹ , a nitrogen-containing aromatic heterocycle containing ^{N or N +} in the constituent atoms of the ring represented by ^{ring T 2} , and the number of carbon atoms represented by ^{rings T 5 and T 6.} The 6 to 20 aromatic hydrocarbon rings may have a substituent. Examples of the substituent include an oxo group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; a nitro group; a cyano group; and a −N (R ^a1 ) (R ^a2 ) group (in the formula, R ^a1 and R). ^a2 is the same as above); hydroxy group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; sulfanyl group; alkylsulfanyl group having 1 to 6 carbon atoms such as methyl sulfanyl group and ethyl sulfanyl group; carboxy group Carbamoyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; sulfo group; sulfamoyl group; alkoxysulfonyl group having 1 to 6 carbon atoms such as methoxysulfonyl group and ethoxysulfonyl group; etc. Can be mentioned.

In formula (I), ring T ^{1 is bonded to L 1} and a carbon atom at a portion where two arbitrary hydrogen atoms contained in ring T ^{1 are eliminated, and ring T 2} is arbitrary contained in ring T ^2. At the portion where two hydrogen atoms are eliminated, it ^{is bonded to L 2} and a carbon atom.
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 the hydrocarbon having 1 to 8 carbon atoms. Examples thereof include divalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms and divalent aromatic hydrocarbon groups 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 and a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms.

The divalent chain aliphatic hydrocarbon groups are methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group and pentane-1,5. Examples thereof include an alkanediyl group such as a −diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group.
Examples of the divalent alicyclic hydrocarbon group include cyclopropane-1,1-diyl group, cyclopropane-1,2-diyl group, cyclobutane-1,1-diyl group, cyclobutane-1,2-diyl group, and the like. Cyclobutane-1,3-diyl group, cyclopentane-1,1-diyl group, cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,1-diyl group, cyclohexane- Examples thereof include a 1,2-diyl group, a cyclohexane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a group represented by the formulas (La1) to (La6).

The divalent aromatic monocyclic 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 o. Examples thereof include a-phenylene group, an m-phenylene group, a p-phenylene group, and groups represented by the formulas (L-b1) to (L-b6).

The ^{divalent hydrocarbon groups having 1 to 8 carbon atoms represented by L 1} and L ² are preferably divalent aliphatic hydrocarbon groups having 1 to 8 carbon atoms or divalent aromatic groups having 6 to 8 carbon atoms. It is a group hydrocarbon group, 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, and even more preferably 1 carbon number. An alkanediyl group of ~ 8 or a divalent aromatic monocyclic hydrocarbon group having 6-7 carbon atoms, particularly preferably a linear alkanediyl group having 1-8 carbon atoms or a divalent aromatic monocyclic hydrocarbon group having 6 carbon atoms. It is a group monocyclic hydrocarbon group.
The divalent aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

The ^{divalent hydrocarbon group having 1 to 8 carbon atoms in L 1} and L ² may have a substituent, and the substituent may be a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom. Nitro group; cyano group; amino group; hydroxy group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; sulfanyl group; alkylsulfanyl group having 1 to 6 carbon atoms such as methyl sulfanyl group and ethyl sulfanyl group. Carboxy group; carbamoyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; sulfo group; sulfamoyl group; alkoxysulfonyl group having 1 to 6 carbon atoms such as methoxysulfonyl group and ethoxysulfonyl group. ; Etc. can be mentioned.
It is more preferable that the divalent hydrocarbon group has no substituent.

L ¹ and L ² are independently, preferably methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, formulas (L-b1) to formulas (L-b6). Group represented by, o-phenylene group, m-phenylene group or p-phenylene group, more preferably methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, It is an o-phenylene group, an m-phenylene group or a p-phenylene group. L ¹ and L ² may be the same or different, but are preferably the same.

k is preferably 3 or less, more preferably 2 or less. In the formula (I), the carbon-carbon double bond indicated by the arrows s and t may have either an E configuration or a Z configuration. That is, formula (I) is defined as including all geometric isomers resulting from the carbon-carbon double bond indicated by arrows s and t, formula (II), formula (III-A) and formula (III-). The same applies to B).

Examples of ^n- valent metal ions represented by M n + include alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion, and barium ion; titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, and cobalt ion. , Transition metal ions such as nickel ion and copper ion; typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion and bismuth ion; and the like.
n is preferably 4 or less, more preferably 3 or less, and even more preferably 2.

Since compound (I) has a valence of 0, that is, an electrically neutral compound, ^{the number r of M n +} is selected so that the valence of compound (I) is 0. r is preferably 1 or 2, and more preferably 1.

For ^{Mn +} , alkaline earth metal ions or main group metal ions are more preferable, magnesium ions, barium ions or aluminum ions are more preferable, and barium ions or aluminum ions are even more preferable.

Compound (I) is preferably a compound represented by the formula (II) (hereinafter, may be referred to as compound (II)).

[In 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 heterocycle which may have a substituent.
Ring T ⁴ represents a nitrogen-containing aromatic heterocycle containing ^{N or N +} as a constituent atom of the ring which may have a substituent.
L ³ represents a single bond or -CO-.
L ⁴ represents a double bond or -CO-. ]

The nitrogen-containing aromatic heterocycle represented by ring T ³ is a nitrogen-containing aromatic heterocycle containing a nitrogen atom as a component of the ring, and the nitrogen atom is> N−, and the ring-forming atom has π electrons. The ring T ³ is preferably 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).
A nitrogen-containing aromatic heterocycle containing N or N +} in the constituent atoms of the ring represented by ring T ⁴ contains a nitrogen atom as a constituent element of the ring, and the nitrogen atom is −N <or> N ⁺ <. , A nitrogen-containing aromatic heterocycle in which the ring-forming atom has π electrons, and the ring T ⁴ is represented by the formula (T ^4- A), the formula (T ^4- B), the formula (T ^4- C) or A ring represented by the formula (T- ^{4-D) is preferable.}
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 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 bond with L 1} or L ^2, and * C means a bond with a carbon atom. ]

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

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

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

[In 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 formulas (I-1) to (I-189) shown in Tables 1 to 3. The compound (I) is preferably a compound represented by the formulas (I-1) to (I-63) and the formulas (I-127) to (I-168), and more preferably the formula (I-). 43) -formula (I-63), formula (I-127) -formula (I-133), formula (I-148) -formula (I-154), and more preferably the formula (I-154). It is a compound represented by the formulas I-43) to (I-54), formula (I-131) to formula (I-133), and formula (I-152) to formula (I-154).

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

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

The compound represented by the formula (I) includes a compound represented by the formula (pt3), a halide containing an n-valent metal ion (preferably chloride), a hydroxide, an acetate, and a phosphate. , Sulfate, silicate, cyanide and the like.
Further, L ¹ and L ² are the same, and ring T ¹ and ring T ² are the same except for> N-CH <⇔> N ⁺ = C <in each ring (pt3). The compound represented by the above 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 this reaction, the amount of the compound represented by the formula (pt1) to be used is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt2).

[In formula (pt2), R ^c is a hydrogen atom, a nitro group or a halogen atom. k is the same as above.
In formula (pt1), formula (pt3) and formula (I), ring T ¹ , 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 0.1 to 150 parts by mass, more preferably 1 to 100 parts by mass, and 5 to 80 parts by mass with respect to 100 parts by mass of the resin (B). Is more preferable.

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

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified by the Color Index (published by The Society of Dyers and Colorists) as having hues other than pigments, and known dyes described in dyeing notes (Dyeing Co., Ltd.). Be done. According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, coumarin. Examples include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

As the pigment (A2), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Blacks 1 and 7.

The content of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, still more preferably 1 to 50% by mass, based on the total amount of solids. %.
The content of the compound (I) is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more based on the total amount of the colorant (A).
Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored resin composition. The total amount of solids and the content of each component relative to the total amount can be measured 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 at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter, "(a)"). A resin having a structural unit derived from) is more preferable. The resin (B) is a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”). Structural units derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"), and side. It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

Specifically, as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, oxalic acid mono [2- (meth). ) Acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.

(B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group. ..
In addition, in this specification, "(meth) acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, and 3-ethyl-3-. Examples thereof include (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( Meta) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane-. Examples thereof include 8-yl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like, and preferred methods thereof. Pysiene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable.

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

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. ..
The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 150 mg-KOH / g, and even more preferably 40 to 135 mg-KOH / g in terms of solid content. Here, 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 by titration using, for example, an aqueous potassium hydroxide solution. ..

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solids.

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 that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa ( Meta) acrylate and the like can be mentioned.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and 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 7 to 65% by mass, more preferably 13 to 60% by mass, based on the total amount of solids. , More preferably 17 to 55% by mass.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholino-1-( 4-Methylsulfanylphenyl) Propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenylketone, 2,4-bis (trichloromethyl) ) -6-Piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl Biimidazole and the like can be mentioned.

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30% by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts, more preferably 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

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

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-Phenylglycine and the like.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to 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 usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

As a solvent
Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (intramolecular-COO- Solvent containing-and not containing -O-);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solves containing -O- in the molecule and not containing -COO-). );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (intramolecular-COO- Solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone (solvents containing -CO- in the molecule and not -COO-);
Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-);
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and the like.
As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

When the solvent (E) is contained, 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 colored resin composition of the present invention. .. In other words, the total solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

The colored resin composition of the present invention may contain a leveling agent (F).

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK), etc. Can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, based on the total amount of the colored resin composition. It is 0.1% by mass. The content of the pigment dispersant is not included in this 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 contains, if necessary, additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like. It may be.

<Manufacturing method of colored resin composition>
The colored resin composition of the present invention comprises a colorant (A) and a resin (B), as well as a polymerizable compound (C), a polymerization initiator (D), a polymerization initiator (D1), and a solvent, which are used as needed. It can be prepared by mixing (E), a leveling agent (F) and other components.

<Manufacturing method of 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. Above all, the photolithography method is preferable.

When the coloring resin composition contains the compound (I) as a coloring agent, a color filter having particularly excellent contrast and light resistance can be produced. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the colored resin composition of the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

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 mixed at room temperature. Then, after adding 8 parts of triethylamine, the mixture was stirred at 40 ° C. for 5 hours. After completion of the reaction, 100 parts of ethyl acetate was added to precipitate crystals, and the mixture was filtered. The crystals were washed 3 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 represented by the 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 solution (aqueous solution 2) in which 19.5 parts of barium chloride dihydrate was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was added dropwise to the aqueous solution 1 at 40 ° C. over 2 hours, and then for 4 hours. Stirred. After cooling, the mixture 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 solution (aqueous solution 2) in which 7.1 parts of aluminum hydroxide was dissolved in 80 parts of water was prepared, the aqueous solution 2 was added dropwise to the aqueous solution 1 at 40 ° C. over 2 hours, and then the mixture was stirred for 4 hours. After cooling, the mixture was filtered, 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 the compound represented by the 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 solution (aqueous solution 2) in which 12.2 parts of barium dihydrate chloride was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was added dropwise to the aqueous solution 1 at 40 ° C. over 2 hours, and then stirred for 4 hours. bottom. After cooling, the mixture was filtered, 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 the formula (I-131).

[Synthesis Example 1]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] A solution of 289 parts of a mixture of decan-9-ylacrylate (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) in 125 parts of propylene glycol monomethyl ether acetate was dissolved in 125 parts using a dropping pump. It was added dropwise over about 5 hours. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate is added dropwise into the flask over about 6 hours using another dropping pump. bottom. After completion of the dropping, 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 weight average molecular weight Mw of the obtained copolymer was 9200, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (B-2) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by gel permeation chromatography (GPC method) under the following conditions.
Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made 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
[Preparation of dispersion liquid (P-1)]
10 parts of the compound represented by the formula (I-52), 4 parts of the solid content of the dispersant BYK-LP N6919 (manufactured by BYK), and the solid content of the resin (B-2) solution (solid content 35.0%). After weighing 5 parts and 181 parts of propylene glycol monomethyl ether acetate, add 300 parts of 0.4 μm zirconia beads, shake for 6 hours using a paint conditioner (manufactured by LAU), and remove the zirconia beads by filtration. A dispersion liquid (P-1) was prepared.
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 4 to obtain a colored resin composition.

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

樹脂（Ｂ−２）：樹脂（Ｂ−２）（固形分換算）
重合性化合物（Ｃ−１）：ジペンタエリスリトールヘキサアクリレート（カヤラッド（登録商標）ＤＰＨＡ；日本化薬（株）製）
重合開始剤（Ｄ−１）：Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン（イルガキュア（登録商標）ＯＸＥ ０１；ＢＡＳＦ社製）
溶剤（Ｅ−１）：プロピレングリコールモノメチルエーテルアセテート In Table 4, each component represents the following compound.
Colorant (A-1): Compound represented by the formula (3)

Resin (B-2): Resin (B-2) (solid content conversion)
Polymerizable compound (C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization Initiator (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE 01; manufactured by BASF)
Solvent (E-1): Propylene glycol monomethyl ether acetate

Example 5
[Preparation of dispersion liquid (P-2)]
In Example 4, the dispersion liquid (P-2) was prepared 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). Made.
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 5 to obtain a colored resin composition.

Example 6
[Preparation of dispersion liquid (P-3)]
In Example 4, the dispersion liquid (P-3) was prepared 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). Made.
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 5 to obtain a colored resin composition.

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

樹脂（Ｂ−２）：樹脂（Ｂ−２）（固形分換算）
重合性化合物（Ｃ−１）：ジペンタエリスリトールヘキサアクリレート（カヤラッド（登録商標）ＤＰＨＡ；日本化薬（株）製）
重合開始剤（Ｄ−１）：Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン（イルガキュア（登録商標）ＯＸＥ ０１；ＢＡＳＦ社製）
溶剤（Ｅ−１）：プロピレングリコールモノメチルエーテルアセテート In Table 5, each component represents the following compound.
Colorant (2-1): Compound represented by the formula (2-1)

Resin (B-2): Resin (B-2) (solid content conversion)
Polymerizable compound (C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)
Solvent (E-1): Propylene glycol monomethyl ether acetate

<Making a colored pattern>
A colored resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then 200 in an oven. Post-baking was performed at ° C. for 20 minutes to obtain a coloring pattern.

<Contrast evaluation>
Regarding the coloring patterns obtained in Example 4 and Comparative Example 1, a contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source; F-10, polarizing film; Tsubosaka The contrast was measured with a blank value of 30,000 using (manufactured by Denki Co., Ltd.). The results are shown in Table 6.

<Light resistance evaluation>
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is placed on the obtained coloring pattern, and xenon is used in a light resistance tester (SUNTEST CPS +: manufactured by Toyo Seiki Co., Ltd.). Irradiate the lamp light for 48 hours, measure the chromaticity of the coloring pattern after irradiation, and use the method described in JIS Z 8730: 2009 (7. Calculation method of color difference) from the measured values to obtain the color difference ΔEab * before and after irradiation. Asked. The chromaticity is measured by measuring the spectrum using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and using the color matching function of the C light source, the xy chromaticity coordinates in the XYZ color system of CIE. (X, y) and the stimulus value Y were measured. The results are shown in Table 7.

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

Claims (4)

Contains colorants and resins
A colored resin composition in which the colorant contains a compound represented by the formula (I).

[In formula (I),
Ring T ¹ is either a ring represented by the formula (R ³ -a1) ~ formula (R ³ -a4).
Ring T ² are, either of the rings of the formula (R ⁴ -a1) ~ formula (R ⁴ -a4).
L ¹ and L ² are independently one of the groups represented by the formulas (L-1) to (L-7).
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 M n +} and is selected so that the valence of the formula (I) is 0. ]

[In formulas (R ^3- a1) to (R ^3-a 4) and formulas (R ^{4-a 1} ) to formula (R ^{4-a 4} ), * L means a bond with ^{L 1} or L ^2. * C means a bond with a carbon atom. ]

[In formulas (L-1) to (L-7), * n means a bond with a nitrogen atom, and * s means a bond with a sulfur atom. ] The colored resin composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition according to claim 1 or 2. A display device including the color filter according to claim 3.