JP6064598B2 - Coloring composition, color filter and display element - Google Patents

Description

  The present invention relates to a colored composition, a color filter, and a display element. More specifically, the present invention is useful for a color filter used for a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored layer, a color filter including a colored layer formed using the colored composition, and a display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There are known methods (for example, Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, Patent Document 4).

  By the way, it is known that it is effective to use a dye as a colorant in order to achieve high luminance and high color purity of a display element or high definition of a solid-state imaging element. Has proposed the use of a triarylmethane dye having a specific structure.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A International Publication No. 2011/162217 Pamphlet

However, according to the study by the present inventors, it has been found that a color filter including a colored layer formed using the colored composition disclosed in Patent Document 5 has a poor balance between heat resistance and solvent resistance.
Therefore, the subject of this invention is providing the coloring composition suitable for formation of the colored layer which can make heat resistance and solvent resistance compatible. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer formed using the said coloring composition, and the said color filter.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a colorant having a specific structure.

  That is, the present invention provides (A) at least one compound selected from the compound represented by the following formula (1) and the compound represented by the formula (2) (hereinafter also referred to as “the present colorant”). The present invention provides a coloring composition containing a coloring agent, (B) a binder resin, and (C) a polymerizable compound (excluding the component (A)).

[In Formula (1),
R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a CH ₂ ═CR ¹⁰ —COO—W— group, or a CH ₂ ═CR ¹⁰ —Ph—W— group. Or CH ₂ ═CR ¹⁰ —CO— group,
R ^{7 to} R ⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
R ¹⁰ represents a hydrogen atom or a methyl group,
Ph represents a phenylene group,
W represents a single bond or a divalent organic group,
l and m each independently represent an integer of 0 to 4;
n represents an integer of 0 to 6,
X ⁻ represents an anion.
However, one or more of R ^{1 to} R ⁶ are CH ₂ ═CR ¹⁰ —COO—W— group, CH ₂ ═CR ¹⁰ —Ph—W— group or CH ₂ ═CR ¹⁰ —CO— group, and l, m And n are not 0 at the same time. ]

[In Formula (2),
R ^{11 to} R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a CH ₂ ═CR ²⁰ —COO—W— group, or a CH ₂ ═CR ²⁰ —Ph—W— group. Or CH ₂ ═CR ²⁰ —CO— group,
R ^{17 to} R ¹⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
R ²⁰ represents a hydrogen atom or a methyl group,
s, t and u each independently represent an integer of 0 to 4,
Ph, W and X ⁻ are synonymous with Ph, W and X ⁻ in formula (1).
However, one or more of R ^{11 to} R ¹⁶ are a CH ₂ ═CR ²⁰ —COO—W— group, a CH ₂ ═CR ²⁰ —Ph—W— group, or a CH ₂ ═CR ²⁰ —CO— group. ]

  Moreover, this invention provides the color filter provided with the colored layer formed using the said coloring composition, and the display element which comprises this color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

  Furthermore, this invention provides the compound represented by the said Formula (1), and the compound represented by Formula (2).

If the colored composition of the present invention is used, a colored layer having both high heat resistance and high solvent resistance can be formed.
Therefore, the colored composition of the present invention has various colors including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for producing a filter.

Hereinafter, the present invention will be described in detail.
Coloring composition Hereinafter, the structural component of the coloring composition of this invention is demonstrated in detail.

-(A) Colorant-
The colored composition of the present invention contains (A) at least one compound selected from the present colorant, that is, the compound represented by the formula (1) and the compound represented by the formula (2), as the colorant. .

First, the anion part in the above formula (1), that is, X ⁻ will be described.
Examples of X ⁻ include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methide anion. Among these, a nitrogen anion is preferable in that a colored layer having high heat resistance can be formed.

  Although it does not specifically limit as said nitrogen anion, The anion represented by following formula (3) is used preferably.

[In Formula (3),
Y ¹ represents a group having a polymerizable group, a group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, or a Y ³ —SO ₂ — group,
Y ³ represents a halo group, a halogenated hydrocarbon group, or a group having a linking group containing a carbon atom, a hydrogen atom, or an atom other than a halogen atom between the C—C bonds of the halogenated hydrocarbon group.
However, when Y ¹ is a Y ³ —SO ₂ — group, Y ³ may be bonded to each other to form a ring. ]

Examples of the halo group for Y ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group in Y ³ include (1) an aliphatic hydrocarbon group, (2) an alicyclic hydrocarbon group, and (3) an alicyclic hydrocarbon as a substituent. Group having an aliphatic hydrocarbon group (hereinafter referred to as “alicyclic hydrocarbon-substituted aliphatic hydrocarbon group”), (4) an aromatic hydrocarbon group, and (5) an aliphatic hydrocarbon group as a substituent. Aromatic hydrocarbon group (hereinafter referred to as “aliphatic hydrocarbon-substituted aromatic hydrocarbon group”), (6) aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as “aromatic hydrocarbon”). And a substituted aliphatic hydrocarbon group ”. The hydrocarbon group constituting the skeleton of Y ³ is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

That is, the (1) aliphatic hydrocarbon group is preferably an alkyl group, and the number of carbon atoms thereof is preferably 1-20, and particularly preferably 1-8. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, neopentyl group , N-hexyl group, n-heptyl group, n-octyl and the like.
The (2) alicyclic hydrocarbon group may be a 2- to 4-ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a norbornyl group, a bornyl group, an adamantyl group, and a bicyclooctyl group.
The (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the total carbon number is preferably 4 to 20, particularly 6 to 14 It is preferable that Specific examples include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclohexylmethyl group, a cyclohexylpropyl group, an adamantylmethyl group, a 1- (1-adamantyl) ethyl group, and a cyclopentylethyl group.
The (4) aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthracenyl group, and the like, and among them, a phenyl group is preferable.
The (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the total carbon number thereof is preferably 7 to 30, and particularly preferably 7 to 20.
The (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the total carbon number thereof is preferably 7 to 30, and particularly preferably 7 to 20. Specific examples include a benzyl group and a phenethyl group.
In addition, the alkyl group in this specification may be linear or branched.

  Among these, the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group includes (1) an aliphatic hydrocarbon group, (3) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, and (4) an aromatic hydrocarbon. Group, (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group, alkyl group, alicyclic saturated hydrocarbon-substituted alkyl group, phenyl group, alkyl-substituted group A phenyl group and an aralkyl group are more preferable, and an alkyl group is particularly preferable.

In Y ³ , the halogen atom in the halogenated hydrocarbon group is preferably a fluorine atom from the viewpoint of heat resistance of the colorant, and the fluorine atom substitutes a part or all of the hydrogen atoms of the hydrocarbon group. May be. By selecting a fluorine atom as a substituent, the anion portion of the colorant becomes a conjugate base of an organic acid having a higher acidity, so that a salt with a stronger ionic bond is formed and heat resistance is increased. Conceivable.

Y ³ may be a group having a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between the C—C bonds of the halogenated hydrocarbon group, but other than a carbon atom, a hydrogen atom or a halogen atom Examples of the linking group containing an atom include —O—, —S—, —CO—, —COO—, —CONH—, —SO ₂ — and the like. And the total carbon number in paragraph [0022] means the total carbon number of the part except the carbon atom which comprises this coupling group.

In the present invention, from the viewpoint of the heat resistance of the colorant, Y ³ includes a halogenated hydrocarbon group or an atom other than a carbon atom, a hydrogen atom, or a halogen atom between C—C bonds of the halogenated hydrocarbon group. A group having a linking group is preferred, a group represented by the following formula (4) or (5) is more preferred, and a group represented by the following formula (4) that forms a conjugate base of an organic acid having a stronger acidity Particularly preferred.

[In Formula (4),
R ³¹ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ³² COOR ³³ — or R ³⁴ COOR ³⁵ CFH—,
R ³² and R ³⁴ independently denote an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group,
R ³³ and R ³⁵ each independently represent an alkanediyl group,
n represents an integer of 1 or more,
“*” Indicates a bond. ]

[In Formula (5),
R ^{41 to} R ⁴⁵ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group or an alkoxy group,
“*” Indicates a bond.
However, at least one of R ^{41 to} R ⁴⁵ is a fluorine atom or a fluorinated alkyl group. ]

In formula (4), the alkyl group for R ³¹ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include the same ones as described above. The fluorinated alkyl group for R ³¹ is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include those obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl groups with fluorine atoms, and perfluoroalkyl groups are particularly preferred.
The alicyclic hydrocarbon group for R ³¹ may be a 2- to 4-ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include the same ones as described above.
As the alkoxy group for R ^31, an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further 1 to 4 carbon atoms is preferable. Specific examples include the same as described above and a 3- (iso-propyloxy) propyloxy group. The fluorinated alkoxy group for R ³³ is preferably a fluorinated alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further 1 to 4 carbon atoms. Specific examples include those in which part or all of the hydrogen atoms of the aforementioned alkoxy group are substituted with fluorine atoms.

R ³² COOR ³³ in R ³¹ -, in R ³⁴ COOR ³⁵ -CFH-, R ³² and R ³⁴ are independently of each other, an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group However, the alkyl group may be linear or branched, and the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specific examples include the same ones as described above. The alicyclic hydrocarbon group may be a 2-4 ring bridged alicyclic hydrocarbon group, and is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group. In addition, as a substituent of an aryl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, or a trifluoromethyl group is mentioned, for example, The position and number of a substituent are arbitrary. Yes, when having two or more substituents, the substituents may be the same or different.
R ³³ and R ³⁵ independently represent an alkanediyl group, but an alkanediyl group having 1 to 6 carbon atoms is preferable. Specific examples include the same ones as described above. Among these, an ethylene group is preferable from the viewpoint of ease of production.

In addition, 10 is preferable and the upper limit of n is more preferable.
R ³¹ is preferably a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ³² COOR ³³ — or R ³⁴ COOR ³⁵ CFH—, particularly a fluorine atom, an alicyclic hydrocarbon group. , A perfluoroalkoxy group, R ³² COOCH ₂ CH ₂ — or R ³⁴ COOCH ₂ CH ₂ CFH— is preferable.
In formula (5), the alkyl group, fluorinated alkyl group and alkoxy group in R ^{41 to} R ⁴⁵ are the same as the alkyl group, fluorinated alkyl group and alkoxy group in R ³¹ of formula (4) described above. A configuration can be employed. However, at least one of R ^{41 to} R ⁴⁵ is a fluorine atom or a fluorinated alkyl group, but at least three of R ^{41 to} R ⁴⁵ are preferably a fluorine atom or a fluorinated alkyl group.

In addition, when Y ¹ is a Y ³ —SO ₂ — group, an embodiment in which Y ³ are bonded to each other to form a ring is also preferable. For example, when Y ³ is a halogenated hydrocarbon group, Y ³ is bonded to each other to form a halogenated alkylene group, and the halogenated alkylene group is particularly preferably a perfluoroalkylene group.

Specific examples of X ⁻ in which Y ¹ is a Y ³ —SO ₂ — group include, for example, anions (a1) and (a2) shown in the following compound group a, and Y ³ is bonded to each other. As what forms a ring, the anion (a3) shown to the compound group a can be illustrated, for example.

The group having a polymerizable group in Y ¹ is not particularly limited, but an organic group having a polymerizable group is preferable. Examples of the organic group include a chain organic group and a cyclic organic group, and the bonding position and the number of bonds of the polymerizable group with respect to these organic groups are arbitrary. In addition, when the organic group has a substituent other than the polymerizable group, the type, bond position, and bond number are not particularly limited.

  Although it does not specifically limit as group which has a polymeric group, For example, group represented by following formula (I) can be mentioned.

[In Formula (I), L ¹ represents a single bond or a divalent organic group, Q ¹ represents a polymerizable group, and “*” represents a bond to N ⁻ . ]

As the divalent organic group represented by L ¹ , a group formed by combining a divalent hydrocarbon group, a divalent hydrocarbon group, and a linking group containing an atom other than a carbon atom and a hydrogen atom, or these And a group in which part of the hydrogen atoms in the group is substituted with a halogen atom. Examples of such an organic group include an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene alkanediyl group having 7 to 20 carbon atoms, or an alkanediyl group having 1 to 10 carbon atoms. At least one selected from a group and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -COO-, -CONR ^a- (R ^a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. And a group formed by combining at least one selected from —SO ₂ — and the like.

Specific examples of the alkanediyl group include an octane-1,8-diyl group, decane-1,10-diyl group, etc., in addition to the above-mentioned alkanediyl group having 1 to 6 carbon atoms. Among these, an alkanediyl group having 2 to 8 carbon atoms is preferable, and an alkanediyl group having 2 to 6 carbon atoms is more preferable.
Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthryl group. Among them, an arylene group having 6 to 10 carbon atoms is preferable, and a phenylene group is particularly preferable.
An arylene alkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group. As the arylenealkanediyl group, an arylenealkanediyl group having 7 to 15 carbon atoms is preferable, and an arylenealkanediyl group having 7 to 13 carbon atoms is more preferable from the viewpoint of availability of raw materials and production. Specific examples include phenylene C _1-6 alkanediyl groups such as a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, a phenylenepentamethylene group, and a phenylenehexamethylene group. The arylenealkanediyl group includes ortho, meta, and para isomers, and is preferably a para isomer from the viewpoint of less steric hindrance.

And at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -COO-, -CONR ^a- (R ^a is a hydrogen atom Or an alkyl group having 1 to 8 carbon atoms) and a group formed by combining at least one selected from —SO ₂ — and an alkanediyl group having 1 to 10 carbon atoms and an arylene having 6 to 20 carbon atoms. A group formed by combining at least one selected from a group and at least one selected from —O—, —COO—, and —SO ₂ — is preferable, and is an alkanediyl group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. A group formed by combining at least one selected from 20 arylene groups and at least one selected from —O— and —SO ₂ — is more preferable.

  Of the groups having such a polymerizable group, a group represented by the following formula (II) is more preferable.

In [Formula (II), L ² represents an arylene group having 1 to 10 carbon atoms, arylene alkanediyl group, or an alkanediyl group and arylene group having 6 to 20 carbon atoms having 1 to 10 carbon atoms having 7 to 20 carbon atoms And a group formed by combining —O— with at least one selected from: Q ¹ and * are as defined above. ]

In the formula (II), specific examples of the arylene group and the arylenealkanediyl group in L ² include the same as those described above, and the preferred embodiments are also as described above.
The group formed by combining at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms with —O— is C _6-20 aryleneoxy C _1-6 alkanediyl. group is preferred, for example, C _6-20 arylene oxymethylene group, C _6-20 arylene-oxy dimethylene group, C _6-20 arylene oxy trimethylene group, C _6-20 arylene oxytetramethylene group, C _6-20 arylene Examples thereof include oxyheptamethylene group, C _{6-20 aryleneoxyhexamethylene} group, and more specifically, phenoxymethylene group, phenoxydimethylene group, phenoxytrimethylene group, phenoxytetramethylene group, phenoxyheptamethylene group, phenoxy. Mention may be made of phenoxy C _1-6 alkanediyl groups such as a hexamethylene group.

There is no particular limitation on the polymerizable group represented by Q ^1, for example, ethylenically unsaturated group, and a trialkoxysilyl group, etc. Examples of the ethylenically unsaturated group, (meth) An acryloyloxy group, a vinyl group, an allyl group, etc. can be mentioned.

The three alkoxy groups constituting the trialkoxysilyl group may be the same or different, but are preferably the same from the viewpoint of ease of production. Examples of such trialkoxysilyl groups include trimethoxysilyl group, triethoxysilyl group, tripropoxysilyl group, tri-n-butoxysilyl group, tri-tert-butoxysilyl group, tri-n-hexyloxysilyl group, A tri-n-octyloxysilyl group etc. can be mentioned. Among these, a tri C _1-8 alkoxysilyl group and a tri C _1-4 alkoxysilyl group are preferable, and a trimethoxysilyl group is particularly preferable.

The polymerizable group represented by Q ¹ is preferably a vinyl group, a (meth) acryloyloxy group, or a trialkoxysilyl group.

Specific examples of X 1 ⁻ in which Y ¹ is a group having a polymerizable group include, for example, the following compound group b and anions represented by the following formula (c1).

  In the compound group b, q represents an integer of 1-20.

The group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton in Y ¹ is not particularly limited, but an organic group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton is preferable. Examples of the organic group include a chain organic group and a cyclic organic group, and the bonding position and the number of bonds of the heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton in the organic group are arbitrary. In addition, when the organic group has a substituent other than the heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, the type, bonding position, and number of bonds are not particularly limited.

  Examples of the group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton include a group represented by the following formula (III).

[In Formula (III), L ³ represents a single bond or a divalent organic group, Q ² represents a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, and “*” represents a bond to N ^−. Indicates. ]

Examples of the divalent organic group represented by L ³ include a divalent hydrocarbon group. Specifically, the same thing as the bivalent hydrocarbon group in L < ¹ > can be mentioned, A preferable aspect is also the same.

  Of the groups containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, a group represented by the following formula (IV) is particularly preferable.

[In the formula (IV), L ³ , Q ² and * are as defined above. ]

  Examples of the heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton in the present invention include a lactam ring and a heterocyclic group shown in the following compound group d. However, in the formula, “*” indicates a bond.

  In the above formula, Z is independently of each other a hydrogen atom; a halogen atom; an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; a formyl group; a hydroxyl group; a carboxyl group; a cyano group; An amino group; an acyl group having 2 to 7 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; an alkylamino group having 1 to 6 carbon atoms; a dialkylamino group having 2 to 8 carbon atoms An alkoxycarbonylalkyl group having 3 to 7 carbon atoms; an alkylthio group having 1 to 6 carbon atoms; an alkylsulfonyl group having 1 to 6 carbon atoms; and an alkylcarbonylamino group having 2 to 6 carbon atoms.

  Specific examples of the halogen atom, the alkyl group having 1 to 8 carbon atoms, and the alkoxy group having 1 to 8 carbon atoms are the same as those described above. Specific examples of the acyl group having 2 to 7 carbon atoms include acetyl group, propiol group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, heptanoyl group and the like. Specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. Specific examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxy. A carbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc. are mentioned. Specific examples of the alkylamino group having 1 to 6 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group. Specific examples of the dialkylamino group having 2 to 8 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-n-butylamino group, and the like. Specific examples of the C3-C9 alkoxycarbonylalkyl group include, for example, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylethyl group, a phenoxycarbonylmethyl group, a phenoxycarbonylethyl group, and the like. Can be mentioned. Specific examples of the alkylthio group having 1 to 6 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, a tert-butylthio group, a sec-butylthio group, an n-pentylthio group, and an n-hexylthio group. Specific examples of the alkylsulfonyl group having 1 to 6 carbon atoms include, for example, methylsulfonyl group, trifluoromethylsulfonyl group, ethylsulfonyl group, pentafluoroethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, and n-butylsulfonyl. Group, tert-butylsulfonyl group, sec-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group and the like. Specific examples of the alkylcarbonylamino group having 2 to 6 carbon atoms include, for example, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group, n-butylcarbonylamino group, tert-butylcarbonyl. An amino group, a sec-butylcarbonylamino group, an n-pentylcarbonylamino group, etc. can be mentioned. Moreover, these Z can also have a substituent, and examples of such a substituent include a hydroxyl group, an amino group, and a thiol group.

  Among these, a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms are preferable, and an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms are more preferable. .

Among the groups containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, a group containing a heterocyclic group having a five-membered ring structure containing a nitrogen atom and an oxygen atom is preferable. ), A group containing a heterocyclic group in which L ³ is a single bond and Q ² is represented by the following formula (V) is preferable.

[In the formula (V), “*” represents a bond with SO ₂ . ]

As a specific example of X ⁻ which is a group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton as Y ¹ , for example, an anion represented by the following formula (d1) can be exemplified.

Among these Y ¹ , a group having a polymerizable group, a group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton is preferable, and the group represented by the formula (II) and the formula (IV) are preferred. Particularly preferred are the groups

  Next, the cation part in Formula (1) is demonstrated. In addition, although various resonance structures exist in the cation part of the compound represented by Formula (1) and the cation part of the compound represented by Formula (2), in this specification, it represents with each formula. When a resonance structure exists in the cation part, it is equivalent to the cation part represented by the formulas (1) and (2).

Specific examples of the alkyl group having 1 to 8 carbon atoms in R ^{1 to} R ^{9 according} to the above formula (1) and R ^{11 to} R ^{19 according} to the above formula (2) include the same as those described above. it can. Among them, the alkyl group of the R ¹ to R ⁶ and R ¹¹ to R ^16, preferably an alkyl group having 1 to 4 carbon atoms, a methyl group or an ethyl group is particularly preferred.
R ^{7 to} R ⁹ and R ^{17 to} R ¹⁹ are preferably an alkyl group having 1 to 4 carbon atoms or a chlorine atom, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
Ph represents a phenylene group, and the phenylene group includes an o-phenylene group, an m-phenylene group, and a p-phenylene group. Ph is preferably a p-phenylene group because it has little steric hindrance.
Examples of the divalent organic group represented by W include a divalent hydrocarbon group, a divalent hydrocarbon group, a group formed by combining a linking group containing an atom other than a carbon atom and a hydrogen atom, or these Mention may be made of groups in which part of the hydrogen atoms of the group has been replaced by halogen atoms. Examples of such an organic group include those similar to the above L ^1, and among them, an alkanediyl group having 1 to 10 carbon atoms, an alkanediyl group having 1 to 10 carbon atoms, and —O— and —S. A group formed by combining at least one selected from — and —COO— is preferable, and a group formed by combining a C 1-10 alkanediyl group, a C 1-10 alkanediyl group and —O—. More preferably, an alkanediyl group having 1 to 8 carbon atoms is preferable, and an alkanediyl group having 1 to 4 carbon atoms is particularly preferable.

In Formula (1), 1 and m are preferably integers of 0 to 2, and n is preferably 0 or 1. However, l, m, and n are not 0 at the same time. Among them, combinations of l, m, and n include l = 1, m = 0, n = 0, l = 0, m = 0, n = 1, l = 2, m = 0, n = 0 combination, l = 1, m = 1, n = 0 combination, l = 1, m = 0, n = 1 combination, l = 1, m = 1, n = 1 combination is preferred, l = A combination of 1, m = 0, n = 0, l = 0, m = 0, n = 1, l = 1, m = 1, n = 0 is more preferable.
In formula (2), one or more of s, t and u are preferably an integer of 1 to 4, more preferably s is an integer of 0 to 2, and t and u are more preferably 0 or 1. . Among them, combinations of s, t, and u include s = 0, t = 0, u = 0, s = 1, t = 0, u = 0, s = 2, t = 0, u = A combination of 0, a combination of s = 1, t = 1, u = 0, a combination of s = 1, t = 1, u = 1, and in particular a combination of s = 1, t = 0, u = 0, The combination of s = 1, t = 1, u = 0 is more preferable.

  Examples of the cation moiety of the compound represented by the formula (1) or the cation moiety of the compound represented by the formula (2) include cations shown in the following compound group e and compound group f. Cations e2, e3, e4, e5, e6, f2, f3, f4, f5 are preferred, and e3, e4, e5, e6, f3, f4, f5 are more preferred.

  The present colorant can be produced by a known method. For example, the same method as the examples in JP-A-2003-206415, JP-T-2007-503477, and JP-A-2008-189925. Can be manufactured. The colorant thus obtained is soluble in various organic solvents including ketones such as cyclohexanone and has excellent heat resistance.

  This coloring agent can be used individually or in mixture of 2 or more types.

  The coloring composition of this invention can contain another coloring agent as (A) coloring agent. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

  As the other colorant, any of pigments, dyes and natural pigments other than the present colorant can be used. From the viewpoint of obtaining pixels with high brightness and color purity, organic pigments and organic dyes are preferable. Organic pigments are more preferred.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), among which JP-A No. 2001-81348 and JP-A No. The rakes described in 2010-026334, 2010-191304, 2010-237384, 2010-237369, 2011-006602, 2011-145346, etc. Pigments;
C. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Pigment orange 38, C.I. I. Organic pigments other than lake pigments such as CI Pigment Violet 23 are preferred.
Among lake pigments, triarylmethane lake pigments, xanthene lake pigments, and azo lake pigments are preferable, and triarylmethane lake pigments and xanthene lake pigments are more preferable.

  The colored composition of the present invention is preferably used for forming a blue pixel. In this case, the (A) colorant preferably contains at least one selected from the group consisting of a blue pigment, a blue dye, a violet pigment, and a violet dye as the other colorant together with the present colorant. In this case, the content ratio of the present colorant is preferably 0.1 to 80% by mass, more preferably 1 to 80% by mass, still more preferably 5 to 70% by mass, and particularly preferably 20% in all colorants. -60 mass%.

  In the present invention, when a pigment is used as another colorant, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  In the present invention, when a pigment is used as another colorant, a known dispersant and dispersion aid can be further contained. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. A dispersant, a polyester-based dispersant, an acrylic-based dispersant and the like, and examples of the dispersion aid include a pigment derivative and the like.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) ), And as a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (manufactured by BYK Corporation (BYK) 76) Lubrizol Co., Ltd.), polyethyleneimine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), polyester dispersant And, Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

  In the present invention, other colorants can be used alone or in admixture of two or more.

  (A) The content ratio of the colorant is usually 5 to 70 mass in the solid content of the coloring composition from the viewpoint of forming a pixel having high heat resistance and high brightness and excellent color purity, or a black matrix having excellent light shielding properties. %, Preferably 5 to 60% by mass. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as an unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100,000. Preferably it is 3,000-50,000. By setting it as such an aspect, heat resistance, a film characteristic, an electrical property, a pattern shape, and the resolution can be made favorable.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts, More preferably, it is 50-350 mass parts, More preferably, it is 100-250 mass parts. By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, and chromaticity characteristic can be made favorable.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 700 parts by weight, and further 100 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. 200-400 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be made favorable.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be made favorable.

-Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
As said solvent, (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has appropriate volatility. You can choose to use.

Among such solvents, for example
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

  Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and the quantity used as 10-40 mass% More preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

  The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP 2008-58642 A, JP 2010-132874 A, and the like. be able to. When both the present colorant and the pigment are used as the colorant, as disclosed in JP 2010-132874 A, after passing the dye solution containing the present colorant through the first filter, A method can be employed in which the dye solution that has passed through the filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. In addition, the present colorant, the above components (B) to (C), and other components used as necessary are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the first filter is used. You may employ | adopt the method prepared by mixing the solution which passed the filter with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Moreover, after passing the dye solution containing this coloring agent through a 1st filter, the dye solution which passed the 1st filter, said (B)-(C) component, and other components used as needed Is mixed and dissolved, the obtained solution is passed through the second filter, the solution that has passed through the second filter is further mixed with the separately prepared pigment dispersion, and the resulting colored composition is mixed with the third filter. It is also possible to adopt a method of preparing by passing through.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or red, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above. In the first method for producing a color filter, any one or more of the blue, green, and red pixel arrays may be a colored layer formed using the colored composition of the present invention.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a blue liquid composition of the thermosetting coloring composition of the present invention is ejected into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

  Next, using the green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which the pixel patterns of the three primary colors of blue, green and red are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above. In the second method for producing a color filter, any one or more of the blue, green, and red pixel arrays may be a colored layer formed using the colored composition of the present invention.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element The display element of this invention comprises the color filter of this invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or IZO (acid value indium and zinc oxide) It is also possible to adopt a structure in which the substrate on which the electrode is formed is opposed to the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  The color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Plane Switching) type, a VA (Vertical Alignment) type, and an OCB (Optical Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

Moreover, the organic EL display element provided with the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of binder resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as “binder resin (B1)”.

<Synthesis of dyes>
Example 1
To a 2 L separable flask equipped with a Teflon stirring blade and a dropping funnel and previously purged with nitrogen, 101 g (0.705 mol) of 1-naphthylamine, 600 mL of methylene chloride, 99.9 g (0.987 mol) of triethylamine were added. It cooled to 0-5 degreeC with the ice bath. While stirring at the same temperature, 177.8 g (0.846 mol) of trifluoroacetic anhydride was added from the dropping funnel over 1 hour, followed by stirring at room temperature for 4 hours. After standing overnight at room temperature, the reaction mixture was transferred to a 5 L beaker, and 600 mL of methylene chloride, ice and about 1 L of 1 mol / L hydrochloric acid were sequentially added and stirred. After confirming that the aqueous layer was acidic, the solution was transferred to a 5 L separatory funnel, the aqueous layer was separated and removed, and the organic layer was washed sequentially with about 1.5 L of saturated aqueous sodium bicarbonate and about 1.5 L of saturated brine. The organic layer was concentrated with a rotary evaporator, and the obtained solid was dried under reduced pressure at 40 ° C. to obtain 165.6 g of a white solid (yield 98%). This compound is referred to as (A1).

In a 100 mL eggplant-shaped flask containing a stir bar, 12.0 g (0.0502 mol) of the compound (A1) obtained above, 10.19 g (0.0668 mol) of 4-chloromethylstyrene, 10.41 g of potassium carbonate (0. 0753 mol) and 50 mL of DMF were added, and the mixture was stirred at 110 ° C. for 15 hours. Thereafter, the reaction mixture was cooled to room temperature, poured into about 500 mL of water, and extracted with ethyl acetate. The obtained organic layer was washed successively with water, 1 mol / L hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was concentrated with a rotary evaporator and dried under reduced pressure at room temperature to obtain 17.41 g of a crude product.
Next, 17.41 g of the crude product, 150 mL of ethanol, 35 mL of ion-exchanged water, and 3.92 g (0.104 mol) of sodium hydroxide were sequentially added to a 300 mL eggplant-shaped flask containing a stirring bar, and stirred at 85 ° C. for 1 hour. . Thereafter, the reaction mixture was cooled to room temperature and concentrated under reduced pressure using a rotary evaporator to distill off ethanol. The obtained mixture was extracted with diisopropyl ether, and the obtained organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure using a rotary evaporator to obtain 12.1 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 10.04 g (0.0419 mol, yield 81%) of a white solid. This compound is referred to as (A2).

  2.17 g (6.16 mmol) of a ketone compound represented by the following formula (A3) synthesized by a method described in JP-A-2011-70171 in a 50 mL eggplant-shaped flask which was previously purged with nitrogen. Compound (A2) 1.55 g (6.47 mmol) and anhydrous toluene 32 mL were added. To this mixture, 2.36 g (15.4 mmol) of phosphoryl chloride was added at room temperature, and the mixture was stirred for 10 hours under a toluene stream under a nitrogen stream. After cooling to room temperature, most of the toluene was distilled off by concentration using a rotary evaporator. The residue was dissolved in chloroform, and the organic layer was washed 3 times with ion-exchanged water and then concentrated under reduced pressure using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 3.20 g (5.08 mmol, yield 82%) of a blue colored solid. This compound is referred to as (A4).

A 100 mL Erlenmeyer flask containing a stir bar was charged with 3.0 g (4.76 mmol) of the above compound (A4) and 2.05 g (7.14 mmol) of bis (trifluoromethanesulfonyl) imide lithium, 30 mL of chloroform, and 15 mL of ion-exchanged water. And stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 3.87 g (4.63 mmol, yield 93%) of a compound represented by the following formula (A5). . In addition, about this compound, it confirmed that it was a compound represented by a following formula (A5) by measuring a < ¹ > H-NMR spectrum and MS spectrum. Let the obtained compound be a coloring agent (A-1).

Example 2
A 1 L three-neck flask containing a stir bar and pre-substituted with nitrogen was charged with 26.7 g (0.22 mol) of N-ethylaniline, 42.4 g (0.40 mol) of sodium carbonate, 3 g (0.02 mol) of sodium iodide, and polymerization was prohibited. 2,5-di-tert-butylhydroquinone 2.22 g (0.01 mol) and ethanol 400 mL were added as agents. 4-Chloromethylstyrene 30.5g (0.2mol) was added here at room temperature, and it stirred under ethanol reflux conditions for 4 hours under nitrogen stream. After cooling the reaction mixture to room temperature, most of ethanol was distilled off under reduced pressure using a rotary evaporator. About 1 L of ion exchange water was added to the residue, and the mixture was extracted with diisopropyl ether. The obtained organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure using a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 46.0 g (0.0194 mol, yield 97%) of an oily substance. This compound is referred to as (A6).

  In a 50 mL eggplant-shaped flask which was previously purged with nitrogen and containing a stirrer, 7 g (19.9 mmol) of the ketone compound represented by the formula (A3), 5.18 g (21.8 mmol) of the above compound (A6), polymerization As an inhibitor, 0.3 g of 2,5-di-tert-butylhydroquinone and 30 mL of toluene were added. To this mixture, 4.58 g (29.9 mmol) of phosphoryl chloride was added at room temperature, and the mixture was stirred for 9 hours under a reflux of toluene under a nitrogen stream. After cooling to room temperature, most of the toluene was distilled off by concentration using a rotary evaporator. The residue was dissolved in chloroform, and the organic layer was washed three times with ion-exchanged water and then concentrated under reduced pressure using a rotary evaporator to obtain 7.52 g of a blue colored solid (yield 62%). This compound is referred to as (A7).

A 200 mL Erlenmeyer flask containing a stirring bar was charged with 5.0 g (8.21 mmol) of the above compound (A7) and 3.53 g (12.3 mmol) of bis (trifluoromethanesulfonyl) imide lithium, 50 mL of chloroform, and 25 mL of ion-exchanged water. And stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 6.72 g (7.88 mmol, yield: 96%) of a compound represented by the following formula (A8). . In addition, about this compound, it confirmed that it was a compound represented by a following formula (A8) by measuring a < ¹ > H-NMR spectrum and a MS spectrum. Let the obtained compound be a coloring agent (A-2).

Comparative Synthesis Example 1
Into a 100 mL Erlenmeyer flask containing a stirring bar, C.I. I. Charge 5.0 g (9.72 mmol) of Basic Blue 7 and 4.19 g (14.6 mmol) of bis (trifluoromethanesulfonyl) imide lithium, add 50 mL of chloroform and 25 mL of ion-exchanged water, and stir at room temperature for about 2 hours. did. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 5.88 g (7.78 mmol, yield: 80%) of a compound represented by the following formula (A9). . Let the obtained compound be a coloring agent (A-3).

Comparative Synthesis Example 2
A 100 mL Erlenmeyer flask containing a stirrer was charged with 5.21 g (10.0 mmol) of a compound represented by the following formula (A10) and 4.31 g (15.0 mmol) of bis (trifluoromethanesulfonyl) imidolithium, and 50 mL of chloroform, 25 mL of ion exchange water was added and stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 7.42 g (9.70 mmol, yield 97%) of a compound represented by the following formula (A11). . Let the obtained compound be a coloring agent (A-4).

Comparative Synthesis Example 3
Into a 50 mL eggplant-shaped flask that was previously purged with nitrogen was added a stir bar, 2.00 g (6.16 mmol) of 4,4′-bis (diethylamino) benzophenone, 1.55 g (6.47 mmol) of compound (A2), and 32 mL of anhydrous toluene. Was added. To this mixture, 2.36 g (15.4 mmol) of phosphoryl chloride was added at room temperature, and the mixture was stirred at 85 ° C. for 20 hours under a nitrogen stream. After cooling to room temperature, about 3 g of ethanol was added to the reaction mixture to stop the reaction, and the supernatant was removed by decantation. The resulting viscous solid was washed with a small amount of toluene. The obtained solid was dissolved in ethanol, recovered as a solution, concentrated by a rotary evaporator, dried under reduced pressure at 50 ° C., and ethanol was removed to obtain 4.66 g of a crude product. The resulting crude product was purified by column chromatography using neutral silica gel to obtain 3.50 g (5.81 mmol, 94% yield) of a blue colored solid. This compound is referred to as (A12).

  A 100 mL Erlenmeyer flask containing a stirring bar was charged with 3.0 g (4.98 mmol) of the above compound (A12) and 2.15 g (7.47 mmol) of bis (trifluoromethanesulfonyl) imide lithium, 30 mL of chloroform, and 15 mL of ion-exchanged water. And stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 3.77 g (4.63 mmol, yield 93%) of a compound represented by the following formula (A13). . Let the obtained compound be a coloring agent (A-5).

<Preparation of dye solution>
Preparation Example 1
15 parts by mass of the colorant (A-1) and 85 parts by mass of cyclohexanone were mixed to prepare a dye solution (A-1).

Preparation Examples 2-5
In Preparation Example 1, dye solutions (A-2) to (A-2) to (A-2) were used in the same manner as Preparation Example 1, except that the colorants (A-2) to (A-5) were used instead of the colorant (A-1). A-5) was prepared.

<Preparation of pigment dispersion>
Preparation Example 6
As a coloring agent, C.I. I. 15 parts by weight of CI Pigment Blue 15: 6, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Was used to prepare a pigment dispersion (a-1).

<Preparation and evaluation of coloring composition>
Preparation of coloring composition Example 3
13.5 parts by mass of pigment dispersion (a-1) and 7.2 parts by mass of dye solution (A-1) as colorants, 9.9 parts by mass of binder resin (B1) solution as binder resin (C) ) 15.4 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, and 2-benzyl-2-dimethyl as a photopolymerization initiator 1.8 parts by mass of amino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) and NCI-930 (produced by ADEKA) 0. 1 part by mass, 0.2 parts by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and as a solvent Propylene glycol monomethyl ether acetate was mixed to prepare a colored composition (S-1) having a solid concentration of 20% by mass.

Evaluation of Chromaticity Characteristics The obtained colored composition was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 200 ° C. for 30 minutes to form a cured film for evaluation.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.080 were obtained. The evaluation results are shown in Table 1. It can be said that the higher the stimulus value (Y), the higher the luminance.

Evaluation of heat resistance The colored composition (S-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a dot pattern on the substrate.
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured.
Next, after the substrate was additionally baked at 230 ° C. for 90 minutes, the chromaticity coordinate value (x, y) and the stimulus value (Y) were measured, and the color change before and after the additional baking, that is, ΔE ^* _ab was evaluated. . As a result, the case where the value of ΔE ^* _ab was less than 3.0 was evaluated as “◯”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 1. It can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

Evaluation of solvent resistance The colored composition (S-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then heated at 90 ° C. The plate was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a dot pattern on the substrate. Thereafter, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C. for 40 minutes.
The chromaticity coordinate values (x, y) and stimulus values (Y) before and after immersion were measured, and the color change before and after immersion, that is, ΔE ^* _ab was evaluated. As a result, the case where the value of ΔE ^* _ab was less than 3.0 was evaluated as “◯”, the case of 3.0 or more and less than 5.0 was evaluated as “Δ”, and the case of 5.0 or more was evaluated as “x”. The evaluation results are shown in Table 1. It can be said that the smaller the ΔE ^* _ab value, the better the solvent resistance.

Example 4 and Comparative Examples 1-3
In Example 3, a colored composition was prepared in the same manner as in Example 3 except that the dye solutions (A-2) to (A-5) were used instead of the dye solution (A-1). Then, the obtained colored composition was evaluated in the same manner as in Example 3. The evaluation results are shown in Table 1.

Claims (7)

(A) colorant comprising a compound represented by the following formula (1), (B) a binder resin and (C) a polymerizable compound (however, the exception of component (A).) Coloring composition containing.

[In Formula (1),
R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a CH ₂ ═CR ¹⁰ —COO—W— group, or a CH ₂ ═CR ¹⁰ —Ph—W— group. Or CH ₂ ═CR ¹⁰ —CO— group,
R ^{7 to} R ⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
R ¹⁰ represents a hydrogen atom or a methyl group,
Ph represents a phenylene group,
W represents a single bond or a divalent organic group,
l and m each independently represent an integer of 0 to 4;
n represents an integer of 0 to 6,
X ⁻ represents an anion.
However, one or more of R ^{1 to} R ⁶ are CH ₂ ═CR ¹⁰ —COO—W— group, CH ₂ ═CR ¹⁰ —Ph—W— group or CH ₂ ═CR ¹⁰ —CO— group, and l, m And n are not 0 at the same time. ] The coloring composition according to claim 1, wherein X ⁻ is an anion represented by the following formula (3).

[In Formula (3),
Y ¹ represents a group having a polymerizable group, a group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, or a Y ³ —SO ₂ — group,
Y ³ represents a halo group, a halogenated hydrocarbon group, or a group having a linking group containing a carbon atom, a hydrogen atom, or an atom other than a halogen atom between the C—C bonds of the halogenated hydrocarbon group.
However, when Y ¹ is a Y ³ —SO ₂ — group, Y ³ may be bonded to each other to form a ring. ] Y ¹ is a group having a polymerizable group, a group containing a heterocyclic group having a nitrogen atom and a carbonyl group in the skeleton, and Y ³ is a halogenated hydrocarbon group or a C—C of a halogenated hydrocarbon group. The coloring composition according to claim 2, which is a group having a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between the bonds.   The colored composition according to claim 2 or 3, wherein the polymerizable group is a vinyl group, a (meth) acryloyloxy group, or a trialkoxysilyl group.   The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-4.   A display device comprising the color filter according to claim 5. A compound represented by the following formula (1).

[In Formula (1),
R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a CH ₂ ═CR ¹⁰ —COO—W— group, or a CH ₂ ═CR ¹⁰ —Ph—W— group. Or CH ₂ ═CR ¹⁰ —CO— group,
R ^{7 to} R ⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
R ¹⁰ represents a hydrogen atom or a methyl group,
Ph represents a phenylene group,
W represents a single bond or a divalent organic group,
l and m each independently represent an integer of 0 to 4;
n represents an integer of 0 to 6,
X ⁻ represents an anion.
However, one or more of R ^{1 to} R ⁶ are CH ₂ ═CR ¹⁰ —COO—W— group, CH ₂ ═CR ¹⁰ —Ph—W— group or CH ₂ ═CR ¹⁰ —CO— group, and l, m And n are not 0 at the same time. ]