JP6473370B2 - Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging device, image display device, colorant, and method for producing colorant - Google Patents

Description

  The present invention relates to a colored composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, a colorant, and a method for producing a colorant.

The coloring composition is used for manufacturing a color filter and the like.
In recent years, color filters tend to be used not only for monitors but also for televisions in liquid crystal display device applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.
Patent Documents 1 to 5 disclose colored compositions containing a compound having a triarylmethane structure (also referred to as a triarylmethane compound).

JP 2011-186043 A JP 2011-6602 A JP 2014-19771 A JP 2014-52436 A International Publication No. 2010-122301

  Triarylmethane compounds have an absorption waveform that is very useful for improving color characteristics, but when applied to the manufacturing process of a color filter, discoloration due to the heating process is a problem. Therefore, in recent years, further improvement in heat resistance of triarylmethane compounds has been demanded.

  As described in Patent Documents 1 to 5, attempts have been made to rake triarylmethane compounds to improve heat resistance, but in the triarylmethane compounds described in Patent Documents 1 to 5, However, satisfactory performance has not yet been obtained.

  Moreover, the triarylmethane type compound described in Patent Document 5 is a dye-type colorant. When the present inventors examined, the heat resistance of the triarylmethane type compound of patent document 5 was inadequate.

  Therefore, an object of this invention is to provide the coloring composition excellent in heat resistance. Another object of the present invention is to provide a cured film, a color filter, a color filter manufacturing method, a solid-state imaging device, and an image display device using the colored composition. Moreover, it aims at providing the manufacturing method of a coloring agent and a coloring agent.

Under such circumstances, as a result of intensive studies by the present inventors, a cation represented by the general formula (1) described later and at least one selected from a tungsten atom, a molybdenum atom, a silicon atom, and a phosphorus atom The inventors have found that a coloring composition having excellent heat resistance can be obtained by using a coloring composition containing a colorant having an anion containing an oxygen atom, and the present invention has been completed. The present invention provides the following.
<1> A coloring composition comprising a colorant and a resin,
The colorant includes a cation represented by the following general formula (1),
An anion containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom, and an oxygen atom;
Coloring composition;
In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 6 to 10 carbon atoms, and R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms. A group or an aryl group having 6 to 10 carbon atoms, R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms, and n1 and n2 each independently represents 0 or 1.
<2> The colored composition according to <1>, wherein the cation is represented by the following general formula (2);
In General Formula (2), R ^1a and R ^2a each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R ^3a represents an alkyl group having 1 to 6 carbon atoms or a carbon number having 6 to 9 carbon atoms. R ^{7 to} R ¹² each independently represents a hydrogen atom, a methyl group, an ethyl group or an isopropyl group.
<3> The colored composition according to <2>, wherein R ^1a and R ^{2a in} the general formula (2) are methyl groups.
<4> At least one selected from an anion of a heteropolyacid containing at least one selected from a tungsten atom and a molybdenum atom and an anion of an isopolyacid containing at least one selected from a tungsten atom and a molybdenum atom The coloring composition according to any one of <1> to <3>, which is a seed.
<5> The colored composition according to any one of <1> to <4>, wherein the anion is at least one selected from a phosphotungstate anion, a silicotungstate anion, and a phosphomolybdate anion.
<6> The colored composition according to any one of <1> to <5>, further including a polymerizable compound.
<7> A cured film obtained by curing the colored composition according to any one of <1> to <6>.
<8> A color filter having the cured film according to <7>.
<9> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <6>, a step of exposing the colored composition layer in a pattern, and coloring And a step of developing and removing an unexposed portion of the composition layer to form a colored pattern.
<10> A solid-state imaging device having the color filter according to <8>.
<11> An image display device having the color filter according to <8>.
<12> The image display device includes at least a red color filter, a blue color filter, and a green color filter, and the blue color filter is the color filter according to <8>. <11> The image display device described in 1.
<13> a cation represented by the following general formula (1);
An anion containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom, and an oxygen atom;
Having a colorant;
In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 6 to 10 carbon atoms, and R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms. A group or an aryl group having 6 to 10 carbon atoms, R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms, and n1 and n2 each independently represents 0 or 1.
<14> a compound having a cation represented by the following general formula (1);
A method for producing a colorant, wherein a compound containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom and an oxygen atom is reacted in a solvent;
In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 6 to 10 carbon atoms, and R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms. A group or an aryl group having 6 to 10 carbon atoms, R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms, and n1 and n2 each independently represents 0 or 1.

  According to the present invention, it is possible to provide a coloring composition having excellent heat resistance. In addition, it has become possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored composition. In addition, it has become possible to provide a colorant having excellent heat resistance.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.
Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Ph represents a phenyl group, and AC represents an acetyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The weight average molecular weight and the number average molecular weight in the present invention are defined as polystyrene converted values by gel permeation chromatography (GPC) unless otherwise specified. GPC removes the solvent from the sample, dilutes the obtained solid content to 0.1% by mass with tetrahydrofuran, and uses TSKgel Super Multipore HZ-H (Tosoh Corporation) with HLC-8020 GPC (manufactured by Tosoh Corporation). A column of three 4.6 mm (inner diameter) × 15 cm (made by Co., Ltd.) connected in series is measured. The conditions are a sample concentration of 0.35% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, a measurement temperature of 40 ° C., and a differential refraction (RI) detector.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content in the present invention is a solid content at 25 ° C.

<Coloring composition>
The colored composition of the present invention (hereinafter also referred to as the composition of the present invention) is at least one selected from a cation represented by the general formula (1) described later, a tungsten atom, a molybdenum atom, a silicon atom, and a phosphorus atom. And a colorant having an anion containing an oxygen atom, and a resin.
By setting it as such a structure, the coloring composition which can form the film | membrane excellent in heat resistance can be provided. This mechanism is presumed to be as follows. Since the cation represented by the general formula (1) has an aryl group (Ar ¹ and Ar ² ) as a substituent on the nitrogen atom bonded to the triarylmethane skeleton, the aryl group forms a bond of the nitrogen atom. It is considered that the p-orbitals of nitrogen atoms are easily shielded by being twisted with respect to the plane. As a result, a compound that acts on the p-orbital of the nitrogen atom to promote the decomposition of the colorant becomes difficult to approach the cation represented by the general formula (1), and the cation is difficult to be decomposed. It is thought that sex is obtained. And since it has an anion containing at least one kind selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom and an oxygen atom, a salt having low solubility in a solvent can be formed, and excellent heat resistance can be obtained. It is thought.
Further, by using the composition of the present invention, a cured film excellent in light resistance, solvent resistance, and voltage holding ratio can also be formed, and such a cured film can be preferably used as a color filter. .
Hereafter, each structure of this invention is demonstrated in detail.

<< Colorant >>
The composition of the present invention has a cation represented by the following general formula (1), an anion containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom, and an oxygen atom. Contains a colorant (hereinafter also referred to as the colorant of the present invention).

<<< Cation >>>>
In the colorant of the present invention, the cation has a structure represented by the following general formula (1).
In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 6 to 10 carbon atoms, and R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms. A group or an aryl group having 6 to 10 carbon atoms, R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms, and n1 and n2 each independently represents 0 or 1.

In General formula (1), Ar < ¹ > and Ar < ² > represent a C6-C10 aryl group each independently. As for carbon number of an aryl group, 6-9 are preferable. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable. The aryl group may be a single ring or a condensed ring.
The aryl group may have a substituent or may be unsubstituted. It preferably has a substituent from the viewpoint of improving heat resistance. Examples of the substituent include the substituents mentioned in the section of Substituent Group A, which will be described later. An alkyl group, an aryl group, and a heteroaryl group are preferable, and an alkyl group is more preferable.
The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. 1-6 are preferable, as for carbon number of an alkyl group, 1-4 are more preferable, and 1-3 are more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group, an ethyl group, and an isopropyl group are more preferable.
(Substituent group A)
Substituent group A includes a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic ring Oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or Arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycal Group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and a silyl group. For details of the substituent group A, the description of paragraph numbers 0174 to 0185 in JP-A-2015-034966 can be referred to, and the contents thereof are incorporated in the present specification.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. 1-6 are preferable, as for carbon number of an alkyl group, 1-4 are more preferable, and 1-3 are more preferable. Specific examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable.

In General Formula (1), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
R ³ is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
R ⁴ is preferably a hydrogen atom.
The alkyl group represented by R ³ and R ⁴ may be linear, branched or cyclic, but is preferably cyclic. 1-10 are preferable, as for carbon number of an alkyl group, 1-9 are more preferable, 1-8 are more preferable, 1-6 are especially preferable, and 6 is the most preferable. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the substituent group A. Specific examples include halogen atoms (for example, chlorine atom, fluorine atom, iodine atom, bromine atom) and the like.
The number of carbon atoms of the aryl groups R ³ and R ⁴ represents the 6-9 is preferred. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the substituent group A. Specific examples include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a halogen atom (for example, a chlorine atom, a fluorine atom, an iodine atom, a bromine atom) and the like.

In the general formula (1), R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms.
n1 and n2 each independently represent 0 or 1, with 0 being preferred.

In the present invention, the cation is preferably represented by the following general formula (2).
In General Formula (2), R ^1a and R ^2a each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R ^3a represents an alkyl group having 1 to 6 carbon atoms or a carbon number having 6 to 9 carbon atoms. R ^{7 to} R ¹² each independently represents a hydrogen atom, a methyl group, an ethyl group or an isopropyl group.

In the general formula (2), R ^1a and R ^2a each independently represent a hydrogen atom, a methyl group, an ethyl group or a propyl group, preferably a methyl group, an ethyl group or a propyl group, and particularly preferably a methyl group.

In General formula (2), R ^<3a > represents a C1-C6 alkyl group or a C6-C9 aryl group.
1-6 are especially preferable and, as for carbon number of an alkyl group, 6 is the most preferable. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the substituent group A. Specific examples include halogen atoms (for example, chlorine atom, fluorine atom, iodine atom, bromine atom) and the like.
The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the substituent group A. Specific examples include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a halogen atom (for example, a chlorine atom, a fluorine atom, an iodine atom, a bromine atom) and the like.

In the general formula (2), R ^{7 to} R ¹² each independently represents a hydrogen atom, a methyl group, an ethyl group or an isopropyl group, preferably a methyl group, an ethyl group or an isopropyl group, more preferably a methyl group or an ethyl group. A methyl group is preferable, and a methyl group is particularly preferable.

In the cation represented by the formula (1), the cation site is present in a delocalized manner as follows. The following structures are synonymous and all are included in the present invention.

Specific examples of the cation represented by the general formula (1) are shown below, but the present invention is not limited thereto.

<<< Anion >>>
In the colorant of the present invention, the anion contains at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom, and an oxygen atom.

In the colorant of the present invention, the anion is from an anion of a heteropolyacid containing at least one selected from a tungsten atom and a molybdenum atom, and an anion of an isopolyacid containing at least one selected from a tungsten atom and a molybdenum atom. At least one selected is preferred. Specific examples of the heteropolyacid and isopolyacid include tungstate anion, molybdate anion, phosphotungstate anion, phosphomolybdate anion, phosphotungsten molybdate anion, silicotungstate anion and tungsten isopolyacid anion. More preferred are tungstate anions, silicotungstate anions and phosphomolybdate anions.
In the present invention, the isopolyacid means a condensed acid having two or more nuclei in which only the transition metal oxo acid is condensed. Further, the heteropolyacid means a condensed acid having two or more nuclei in which an oxo acid of a transition metal oxo acid and an oxo acid of an atom other than the transition metal are condensed.

Examples of the anion of the heteropolyacid or isopolyacid include Keggin phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson phosphotungstate ion (α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β -[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- As other examples, [P ₂ W ₁₇ O ₆₁ ] ¹⁰⁻ , [P ₂ W ₁₅ O ₅₆ ] ¹²⁻ , [H ₂ P ₂ W ₁₂ O ₄₈ ] ¹²⁻ , [NaP ₅ W ₃₀ O ₁₁₀ ] ^{14 -} , Α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , α- [PMo ₁₂ O ₄₀ ] ^3- , α- [PW ₁₁ MoO ₄₀ ] ^3- , α- [PW ₉ Mo ₃ O _{40 ^{] 3-, α- [PW 3 Mo}} 9 O 40] 3-, α- [SiMo 12 O 40] 4-, α- [P 2 ^{_{o 18 O 62] 6-, [}} Mo 2 O 7] 2-, [Mo 6 O 19] 2-, include [Mo ₈ O _26] ^4-, and the like.

Moreover, as an anion, the anion containing 1 or more types chosen from a silicon atom and a phosphorus atom, and oxygen can be used. For example, an anion of an oxo acid having one or more selected from a silicon atom and a phosphorus atom can be mentioned, and specific examples include SiO ₃ ²⁻ , PO ₄ ^{3− and the} like.

From the viewpoint of easy synthesis of the colorant, the anion is a heteropolyacid anion such as a Keggin type phosphotungstic acid anion, a Dawson type phosphotungstic acid anion, a Keggin type silicotungstate anion, [W ₁₀ O ₃₂ ] ^4- etc. Isopolyacid anions are preferred.

  In synthesizing the colorant of the present invention, the compound supplying the anion can be produced by a known and commonly used method, or a commercially available product can be used as it is. Examples of such compounds include corresponding heteropoly acid salts, isopoly acid salts, silicates, and phosphates. As these various salts, monovalent metal salts such as sodium, lithium and potassium are preferable because they are excellent in water solubility and facilitate the synthesis of the colorant.

  In addition, the compound which supplies an anion used when obtaining the coloring agent of this invention may be used individually by 1 type, or may be used with a 2 or more types of mixture. When a mixture of two or more types is used as the compound supplying an anion, a mixture of colorants having different anions is obtained.

  In the colorant of the present invention, the amount dissolved in 100 g of water at 25 ° C. is preferably 0.1 g or less, more preferably 0.01 g or less. The amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25 ° C. is preferably 0.1 g or less, more preferably 0.01 g or less. The colorant of the present invention preferably has a solubility in at least one of water and propylene glycol monomethyl ether acetate in the above range, and more preferably in the above range.

The colorant of the present invention includes a compound having a cation having a structure represented by the general formula (1) (also referred to as compound A), at least one selected from a tungsten atom, a molybdenum atom, a silicon atom, and a phosphorus atom, It can be produced by reacting a compound containing oxygen atoms (also referred to as compound B) in a solvent such as water.
The mixing ratio of compound A and compound B is preferably compound A: compound B = 20: 1 to 1:20, more preferably 1: 5 to 5: 1.
0-90 degreeC is preferable and, as for reaction temperature, 15-60 degreeC is more preferable.
As the reaction (lake formation) proceeds, solids are precipitated, and when the solids have been deposited, filtration is performed, and then the solids are washed and filtered to obtain a wet cake. The wet cake can be made into a powdery or granulated dry powder by dry pulverization. The colorant of the present invention can be used in any form of a wet cake or a dry powder.
Compound A preferably has a dissolution amount in 100 g of water at 25 ° C. of more than 0.1 g, more preferably 1 g or more. Moreover, it is preferable that the amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25 ° C. exceeds 0.1 g, and more preferably 1 g or more. Compound A preferably has a solubility in at least one of water and propylene glycol monomethyl ether acetate in the above range, and more preferably in the above range.
As an example of a specific production method, for example, after dissolving the compound A in water to form an aqueous solution, the aqueous solution and the compound B or an aqueous solution or an aqueous dispersion thereof are theoretically equimolar ratios. (For example, the method of manufacturing by stirring and mixing while heating as needed is mentioned.

  When the colorant of the present invention is used as a color filter colorant, it is preferable that the metal and ionic components are not contained in the colorant as much as possible. This is preferable for the liquid crystal display device. The standard of cleaning is, for example, until the specific conductivity of the cleaning water becomes equal to or less than the specific conductivity of the raw water + 20 μS / cm. In this purification, purification by ion exchange membrane can be used in addition to purification by alkali washing, acid washing and organic solvent washing.

  Examples of the drying after filtration and washing described above include heating by a heat source installed in a dryer, batch-type drying for removing the solvent, and continuous drying. Examples of the dryer include a box dryer, a band dryer, and a spray dryer. The pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles. For example, the dried product has a lamp shape as in the case of drying using a box dryer or a band dryer. And the like, for example, pulverization with a mortar, hammer mill, disk mill, pin mill, jet mill or the like.

When the average particle diameter of the primary particles is 100 nm or less, the colorant thus obtained can be used as it is as the color filter colorant without any special post-process. When the average particle diameter of the primary particles is larger than 100 nm, it is preferable to use the particles after making the particles finer with a kneader, a mix muller, a supermixer, a trimix, a KCK mill, a Hoover muller or the like.
In the present invention, the average particle diameter of primary particles is measured as follows. First, the particle | grains in a visual field are image | photographed with a transmission electron microscope or a scanning electron microscope. And the longest length (maximum length) of the internal diameter of each particle | grain is calculated | required about 50 of the primary particles which comprise the aggregate on a two-dimensional image. The average value of the maximum length of each particle is defined as the average particle size of the primary particles.

As for content of the coloring agent of this invention in the composition of this invention, 1-60 mass% is preferable with respect to the total solid of the composition of this invention. The lower limit is more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 45% by mass or less.
Only 1 type may be used for the coloring agent of this invention, and it may use 2 or more types together. When using 2 or more types together, it is preferable that the sum total is the said range.

<< other colorants >>
The composition of the present invention may further contain another colorant in addition to the colorant of the present invention. Other colorants include dyes, pigments and dispersions thereof. When the pigment is blended as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

  Examples of the dye include azo (for example, Solvent Yellow 162), anthraquinone (for example, an anthraquinone compound described in JP-A No. 2001-10881), and a phthalocyanine (for example, a phthalocyanine compound described in US 2008 / 0076044A1). ), Xanthene series (for example, C.I. Acid Red 289), triarylmethane series (for example, C.I. Acid Blue 7), C.I. Acid Blue 83 (C.I. Acid Blue 90), C.I. Acid Blue 90, C.I. Solvent Blue 38 (C.I. Solvent Blue 38), C.I.・ I Acid By Oret 17 (CI Acid Violet 17), CI Acid Violet 49 (CI Acid Violet 49), CI Acid Green 3 (C.I. Acid Green 3), methine dye, xanthene dye (For example, Unexamined-Japanese-Patent No. 2010-32999), a dipyrromethene type metal complex compound (For example, Unexamined-Japanese-Patent No. 2012-237985) etc. are mentioned.

Examples of pigments include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo Thioindigo, isoindoline, isoindolinone, pyranthrone, or isoviolanthrone. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Disazo condensation compound pigments such as Brown 23, Pigment Yellow 13, Pigment Yellow 83, or Disazo Compound Pigments such as Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15, Pigment Blue 56 Or triarylcarbonium compound pigments such as Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, pigment red 264, pigment red 272, pigment orange 71, or diketopyrrolopyrrole compound pigment such as pigment orange 73, thioindigo compound pigment such as pigment red 88, pigment yellow 139, pigment orange 66 Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Oren 40, or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.
As pigments, blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38 are preferable. Pigment Blue 15: 3, 15: 6 and Pigment Violet 23 are more preferable, and Pigment Blue 15: 6 is more preferable.

  The content of the other colorant can be used within a range not impairing the effects of the present invention, and is preferably 0.5% by mass to 70% by mass with respect to the total solid content of the composition of the present invention. Further, the composition is preferably added to the composition of the present invention so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.

  In particular, the other colorant preferably includes at least one selected from a xanthene dye, a dipyrromethene metal complex compound, an oxazine compound and a phthalocyanine compound, and includes at least one selected from a xanthene dye and a dipyrromethene metal complex compound. More preferably.

<<< Xanthene Dye >>>
A xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. As the xanthene dye, for example, Color Index (CI) Acid Red 51 (hereinafter, CI Acid Red is omitted, and only the number is described. Others are also the same), 52, 87. 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like. The xanthene dye is preferably dissolved in an organic solvent.

  The xanthene dye preferably contains a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”). Compound (1a) may be a tautomer thereof. In the case of using the compound (1a), the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye.

Formula (1a)
In general formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is substituted with —O—, —CO— or —NR ¹¹ —. May be;
R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom;
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ ;
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms;
m1 represents the integer of 0-5. when m1 is 2 or more, the plurality of R ⁵ may be the same or different;
m2 and m3 each independently represents an integer of 0 to 3. when m2 and m3 are each independently 2 or 3, a plurality of R ⁶ and R ⁷ may be independently the same or different;
a represents 0 or 1; when a represents 0, any group of R ^{1 to} R ⁷ has an anion;
X ⁻ represents an anion;
Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different;
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, -CO -, - NH- or -NR ⁸ - may optionally be substituted with, R ⁹ and R ^10, may form a heterocyclic ring of 3 to 10-membered ring containing a nitrogen atom bonded to each other ;
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Of these, a toluyl group, a xylyl group, a mesityl group, and a propylphenyl group are preferable.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, - SO 3 H, -SO 3 - Z +, -CO ₂ H, —CO ₂ R ⁸ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among them, as the _{substituent, -SO 3 -, - SO 3} H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ is preferably, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. The _{^{Z +, -SO 3 - - -SO}} 3 in this case N ⁺ (R ¹¹⁾ ₄ are preferred.
When R ^{1 to} R ⁴ are these groups, a color filter that is superior in heat resistance can be formed.

Examples of the ring formed by combining R ¹ and R ² with each other and the ring formed by combining R ³ and R ⁴ with each other include the following.
Among these, the following structures are preferable from the viewpoint of compound stability.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group , An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.
Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group are preferable, and a propyl group, an isopropyl group, a butyl group, a hexyl group, A 2-ethylhexyl group is preferred.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Of these, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.

Examples of —CO ² R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are preferable.

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2 -Methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.
Among them, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-pentylsulfamoyl group, N -(2-ethylhexyl) sulfamoyl group is preferred, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N- (2-ethylhexyl) A sulfamoyl group is more preferred.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group and a halogen atom.

R ^{5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R 8, -CO 2 NHR 9, -SO 3 -, -SO 3 - Z +, -SO 3 H, -SO 2 R 8 or -SO ₂ NHR ⁹ is _{^{preferably,, -SO 3 -, -SO 3}} - Z +, -SO 3 H or -SO ₂ NHR ⁹ is more preferable.
m1 is preferably an integer of 1 to 4, and more preferably 1 or 2.
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms.
m2 and m3 each independently represents an integer of 0 to 3, and 0 is preferable.
Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

a represents 0 or 1, and when a represents 0, it is preferable that any group of R ^{1 to} R ⁷ has an anion and R ⁵ has an anion.
X ⁻ is included depending on the valence of the cation contained in the general formula (1a), and is usually monovalent or divalent, and monovalent is preferable. Examples of the anion X ⁻ include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a low nucleophilic anion. A fluorine anion, a chlorine anion, a bromine anion or an iodine anion is preferable. . The low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated. Examples of anions include a low nucleophilic anion described in paragraph No. 0075 of JP2007-310315A, anions described in paragraphs 0016 to 0025 of JP2012-173399A, and JP2013-033731A. Examples include the anion moiety described in paragraphs 0025 to 0033, the contents of which are incorporated herein.
Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .
N ⁺ (R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ¹¹ . The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable.

  The compound (1a) is preferably a compound represented by the general formula (3a) (hereinafter sometimes referred to as “compound (3a)”). Compound (3a) may be a tautomer thereof.

In the general formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 3 carbon atoms, and is contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. —CH ₂ — may be substituted with —O—, —CO— or —NR ¹¹ —.
R ³³ and R ³⁴ each independently represents an alkyl group, an alkylsulfanyl group, or an alkylsulfonyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ³¹ and R ³³ may be bonded to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be bonded to each other to form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 each independently. When p is 2 or more, the plurality of R ³³ may be the same or different. When q is 2 or more, the plurality of R ³⁴ may be the same or different.
R ¹¹ has the same meaning as R ¹¹ in the formula (1a).

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ^32, the carbon number of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms described in R ⁸ in the formula (1a) Examples thereof include 1 to 10 monovalent saturated hydrocarbon groups. Of these, methyl, ethyl, propyl, butyl, hexyl and 2-ethylhexyl are preferred. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms described for R ¹ in formula (1a). It is done.
As a C1-C3 alkoxy group in which the hydrogen atom contained in a C6-C10 aromatic hydrocarbon group may be substituted, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

The alkyl group having 1 to 4 carbon atoms in R ³³ and R ^34, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, sec- butyl group, and a tert- butyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.

  p and q are preferably an integer of 0 to 2, and preferably 0 or 1.

  Specific examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43) described in paragraph numbers 0039 to 0046 of JP-A-2014-005451. Are incorporated herein.

  As the xanthene dye, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink R—H / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. . Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material, The content is integrated in this-application specification.

<<< dipyrromethene-based metal complex compound >>>
Examples of the dipyrromethene metal complex compound include compounds in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.

Formula (I)

In general formula (I), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  Examples of the substituent include the substituent group A described above. When the substituent is a group that can be further substituted, it may be further substituted with any of the above-described substituents. In addition, when it has two or more substituents, those substituents may be the same or different.

In general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5-membered, 6-membered or 7-membered A ring may be formed. Examples of the ring formed include a saturated ring and an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered saturated ring or unsaturated ring include a pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the formed 5-membered, 6-membered and 7-membered rings are further substitutable groups, they may be substituted with any of the above-mentioned substituent group A, and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.

In general formula (I), R ¹ and R ⁶ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, a carbonamido group, a ureido group, An alkoxycarbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In general formula (I), R ² and R ⁵ are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, a carbamoylsulfonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, An alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (I), R ³ and R ⁴ are preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.

In the general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl Group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl group. Moreover, it is more preferable than a C1-C12 branched or cyclic alkyl group, for example, an isopropyl group, a cyclopropyl group, i-butyl group, a tert-butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group are mentioned. A secondary or tertiary alkyl group having 1 to 12 carbon atoms is more preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the general formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group includes a 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2 -A benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group or benzotriazol-1-yl group is preferable, and a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group or 1-pyridyl group is more preferable. preferable.

Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, in addition to B, such as, AlCl, InCl, FeCl, TiCl 2, SnCl 2, SiCl 2 Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is more preferable. Particularly preferred. Among these, Zn is particularly preferable.

A preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is described in paragraphs 0153 to 0176 of JP2012-237985A. The complex compounds represented by 1), (I-2) or (I-3) can be taken into consideration, the contents of which are incorporated herein.
As specific examples of the dipyrromethene-based metal complex compound, the description in paragraphs 0179 to 0186 of JP2012-237985A can be referred to, and the contents thereof are incorporated in the present specification.

  When the composition of the present invention contains at least one selected from a xanthene dye and a dipyrromethene metal complex compound, the mass ratio of the total amount of the above-described colorant of the present invention and the xanthene dye and dipyrromethene metal complex compound Is preferably 1.0: 0.05 to 1.0: 1.0, and more preferably 1.0: 0.1 to 1.0: 0.6.

<< polymerizable compound >>
The composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

  Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such compound groups are widely known in this industrial field, and in the present invention, these compounds can be used without any particular limitation. These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
As specific examples of these compounds, paragraph numbers 0156 to 0159 in JP-A No. 2014-208808 can be referred to, and the contents thereof are incorporated in the present specification.

  Moreover, as a polymeric compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial item; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (manufactured by company) KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination. Thus, a method of adjusting both sensitivity and intensity is also effective. Further, the selection and use method of the polymerizable compound is also an important factor with respect to the compatibility and dispersibility with other components contained in the composition of the present invention. Compatibility with more than one species may be improved. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

The content of the polymerizable compound in the total solid content of the composition of the present invention is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, from the viewpoint of more effectively obtaining the effects of the present invention. -60 mass% is particularly preferred.
The composition of the present invention may contain only one type of polymerizable compound or two or more types. When two or more types are included, the total amount is preferably within the above range.

<< photopolymerization initiator >>
The composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
As specific examples of the oxime compound, the description in paragraph 0053 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.

  Moreover, in this invention, the compound represented by the following general formula (1) or general formula (2) is more preferable as an oxime compound from a viewpoint of a sensitivity, the time stability, and the coloring at the time of post-heating.

(In general formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 1 to 5. .)

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating with time, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, para-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthioxy group, an arylthioxy group or an amino group from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. preferable. Moreover, n in General formula (1) has a preferable integer of 1-2.

In the general formula (2), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heterocyclic oxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl. Represents a group, a heterocyclic thiocarbonyl group, a heterocyclic thiocarbonyl group or CO-CO-Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

^R102 represents an alkyl group, an aryl group or a heterocyclic group, which may be substituted.
R ¹⁰³ and R ¹⁰⁴ each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.

R ^{105 to} R ¹¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group. , Alkylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfonic acid group, hydroxy group, carboxylic acid group, amide group, carbamoyl Represents a group or a cyano group.
One or two of R ^{105 to} R ¹¹¹ are electron-withdrawing substituents, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group, or an arylcarbonyl group, which has a much higher curability. Since a coloring composition is obtained, it is preferable.

Specific examples of the compound having a fluorene structure represented by the general formula (2) include compounds described in paragraph numbers 0087 to 0088 of JP 2014-177502 A, the contents of which are described in the present specification. It will be incorporated.
The compound having a fluorene structure represented by the general formula (2) can be synthesized according to a synthesis method described in, for example, WO2014-050738.
Commercially available oxime photopolymerization initiators include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 (manufactured by ADEKA), Adeka Arcles NCI-930 (manufactured by ADEKA) and the like can be used.

  As specific examples of the biimidazole compound, the description in paragraphs 0061 to 0070 of JP2013-182213A can be referred to, and the contents thereof are incorporated in the present specification.

In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the composition of the present invention.
In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.

In the composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 20% by mass of the total solid content of the composition from the viewpoint of more effectively obtaining the effects of the present invention, and 0.5 to 19 mass% is more preferable, and 1-18 mass% is especially preferable.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Resin >>
The composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing the colorant in the composition or the purpose of the binder. Note that a resin mainly used for dispersing a colorant is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.

  The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

  In the composition of the present invention, the resin content is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of resin or two or more types of resins. When two or more types are included, the total amount is preferably within the above range.

<<< Dispersant >>>
In the composition of the present invention, the resin preferably contains a dispersant. As the dispersant, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used.
Examples of the dispersant include linear and multi-branched polymers, specifically acrylic resins, polyurethane resins, polyester resins, etc. Among them, polyurethane resins have a high level of luminance heat resistance. It is preferable because it is higher than a dispersant having another structure.

  Such dispersants are commercially available, eg, Disperbyk-2000, Disperbyk-2001, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182y, -2155, Disperbyk-2164 (manufactured by Big Chemie (BYK)), Solsperse 24000, Solsperse 37000, Solsperse 56000, Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), Addispar PB821, Addispar PB822, Addispar PB823, Addispar PB824, Addispar PB827, Addisper PB880, Addispar PB881 Mention may be made of the Fine-Techno Co., Ltd.), and the like.

  In the present invention, the dispersant is classified as a kind of polyurethane resin. As a backbone polymer, one molecule of linear polyurethane is grafted with two or more molecules composed of polyester and / or polyether as a branch polymer. The comb-shaped polymer having a bonded structure is a comb-shaped polymer composed of a ring-opening polymer having a trunk polymer portion of polyethyleneimine and a branch polymer portion of ε-caprolactone when the color filter is used. It is preferable because it is higher than polymers having other structures.

  Examples of the polyester structure contained in the polyurethane resin include a condensed polyester of hydroxycarboxylic acid, a condensed polyester of various diols and various dicarboxylic acids, and a ring-opening polymer of ε-caprolactone, while the polyether structure is, for example, Examples thereof include an ethylene oxide ring-opening polymer, a propylene oxide ring-opening polymer, a tetrahydrofuran ring-opening polymer, or two or more kinds of random or block ring-opening copolymers selected from ethylene oxide, propylene oxide, and tetrahydrofuran.

  In the dispersant, the urethane bond in the trunk polymer is mainly used as a colorant adsorbing part, and the polyester and / or polyether of the branch polymer is mainly used as a resin compatible part (for example, a part compatible with a polymerizable compound). And excellent heat resistance can be obtained. Of course, if it contains ionized atomic groups such as a salt in which the carboxyl group is neutralized with a base or a salt in which the amino group is neutralized with an acid, these are also added as a secondary agent to the colorant adsorbing part or the resin compatibility. It functions as a part. Examples of the optimum dispersing agent include Disperbyk-182 and Disperbyk-2164.

<<< Alkali-soluble resin >>>
The composition of the present invention can contain an alkali-soluble resin as a resin. By containing an alkali-soluble resin, developability and pattern formation are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

  The alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.

  Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

  The alkali-soluble resin is preferably a linear organic polymer and is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, the alkali-soluble resin in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, and poly (2-hydroxyethyl (meth)). Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.
As the alkali-soluble resin, a copolymer of benzyl methacrylate and methacrylic acid is also preferable.

  As the alkali-soluble resin, a copolymer of maleimide and ethylene oxide as shown in the following formulas (b1) and (b2) can also be preferably used.

(In formula (b1), R ¹ represents a hydrogen atom, an aryl group, or an alkyl group.)
Examples of the alkyl group when R ¹ represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and the like can be mentioned.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxy group, and an amino group.
When R ¹ represents an aryl group, examples of the aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include an alkyl group such as a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group, an alkoxy group such as a methoxy group, Examples thereof include a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.

(In formula (b2), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 or 3 carbon atoms, R ⁴ represents a hydrogen atom, an aryl group, or an alkyl group, m represents an integer of 1 to 15.)

Examples of the alkyl group when R ⁴ represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, a 2-ethylhexyl group, and the like can be given.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.
Examples of the aryl group when R ⁴ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, and a heteroaryl group containing a heteroatom. More specifically, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include an alkyl group such as a nonyl group, a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group, and a methoxy group. Examples thereof include an alkoxy group, a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.

  Further, the alkali-soluble resin may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  In particular, a copolymer having a repeating unit represented by the following general formula (2) and an acidic group is preferred, and more preferably a structural unit represented by the general formula (3) in addition to the general formula (2) and the acidic group. And a copolymer having.

(In General Formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ^{21 to} R ²⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group. )

(In General Formula (3), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an unsaturated double bond having 3 to 20 carbon atoms as a partial structure. R ¹² and R ¹³ are not both hydrogen atoms, and at least one of R ¹² and R ^{13 is} a C 3-20 carbonyl group containing an unsaturated double bond as a partial structure. When represented, it may further contain a carboxy group as a partial structure.)

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

Moreover, alkali-soluble resin may contain the structural unit derived from a compound by following formula (X).
(In Formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

The weight average molecular weight of the alkali-soluble resin is preferably 2,000 to 200,000, more preferably 2,000 to 100,000, and particularly preferably 5,000 to 50,000, from the viewpoints of developability, liquid viscosity, and the like. .
The acid value of the alkali-soluble resin is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, still more preferably 50 to 200 mg / KOH, and particularly preferably 90 to 200 mg / KOH.

<< Organic solvent >>
The composition of the present invention preferably contains an organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when it is used as a colored composition.

  As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used, and specific examples thereof include those described in JP-A-2012-032754, paragraph numbers 0161 to 0162.

  It is also preferable to mix two or more of these organic solvents from the viewpoint of the solubility of each component described above. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate.

In the composition of the present invention, the content of the organic solvent is preferably such that the total solid concentration in the composition is 10 to 80% by mass, and more preferably 15 to 60% by mass.
The composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.

<< Crosslinking agent >>
The composition of the present invention may further contain a crosslinking agent.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with one substituent; Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the descriptions in paragraphs 0134 to 0147 of JP-A No. 2004-295116, the contents of which are incorporated herein.
When the composition of this invention contains a crosslinking agent, 0.01-50 mass% is preferable with respect to the total solid of a composition, More preferably, 0.5-30 mass% It is.

<< Surfactant >>
The composition of the present invention may contain a surfactant. The surfactant may be nonionic, cationic, or anionic, but a surfactant having an ethylene oxide structure and a fluorosurfactant are preferred. In particular, a surfactant having an ethylene oxide structure having an HLB (Hydrophile-Lipophile Balance) value in the range of 9.2 to 15.5 or a fluorine-based surfactant described in JP-A-2-54202 is preferred.
When the composition of this invention contains surfactant, 0.0001-2.0 mass% is preferable with respect to the total solid of a composition, More preferably, 0.005 is content of surfactant. It is -1.0 mass%.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<< Dye stabilizer >>
The composition of the present invention may comprise a dye stabilizer. As the dye stabilizer, a polymer dispersant is preferable. Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt and (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; sulfonic acid or phosphoric acid having a crosslinkable group And the like. As the crosslinkable group, a known polymerizable group that can be cross-linked by a radical, an acid, or heat can be used. Specific examples include (meth) acryl groups, styrene groups, vinyl groups, cyclic ether groups, and methylol groups, with (meth) acryl groups, styrene groups, and vinyl groups being preferred, and (meth) acryl groups and styrene groups being preferred. More preferred.
It is also effective to add bistrifluoromethanesulfonimide sodium salt and the following anion salts (lithium salt, sodium salt, potassium salt, etc.) as a dye stabilizer.
When the composition of the present invention contains a dye stabilizer, the content of the dye stabilizer is preferably 0.01 to 50% by mass, more preferably 0.5%, based on the total solid content of the composition. -30 mass%.

<< Antioxidant >>
The composition of the present invention may contain an antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.
Examples of the radical scavenger include phenolic antioxidants and hindered amine antioxidants. Examples of phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
For example, compounds described in paragraphs 0013 to 0034 of JP2012-155243A and paragraphs 0030 to 0042 of JP2013-14748A can be preferably used.
A peroxide decomposer is a compound that decomposes peroxides generated by exposure to light into harmless substances and prevents the generation of new radicals. For example, phosphorus antioxidants, sulfur And system antioxidants. Among these, sulfur-based antioxidants are preferable from the viewpoint of the stability of color characteristics.
Examples of the ultraviolet absorber include salicylate-based antioxidants and benzophenone-based antioxidants.
A singlet oxygen quencher is a compound that can deactivate singlet oxygen by energy transfer from oxygen in a singlet state. For example, ethylenic compounds such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, 1,4- Amines such as diazabicyclooctane (DABCO), N-ethylimidazole, condensed polycyclic aromatic compounds such as optionally substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene, diphenylanthracene; 1,3-diphenylisobenzofuran In addition to aromatic compounds such as 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenylcyclopentadiene, Harry H. et al. wasserman, “Single Oxygen”, Chapter 5, Academic Press (1979), Nicholas J. et al. Turro, ““ Modern Molecular Photochemistry ””, Chapter 14, The Benjamin Cummings Publishing Co. , Inc. (1978), and CMC Co., Ltd., High Performance Chemicals for Color Photosensitive Materials, Chapter 7 (2002) can include compounds exemplified as singlet oxygen quenchers.
In addition, a metal complex having a sulfur atom-containing compound as a ligand can be exemplified. Examples of such compounds include transition metal chelate compounds such as nickel complexes, cobalt complexes, copper complexes, manganese complexes, and platinum complexes having bisdithio-α-diketone, bisphenyldithiol, and thiobisphenol as ligands. .
Examples of the sulfur antioxidant include thiopropionate compounds and mercaptobenzimidazole compounds. Of these, thiopropionate compounds are preferred from the viewpoint of the stability of color characteristics.

  In this invention, antioxidant can be used individually or in mixture of 2 or more types. The content of the antioxidant is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

<< Reduction inhibitor >>
The composition of the present invention can also contain a reducing inhibitor. As the reduction inhibitor, a quinone compound is preferable, and a quinone compound having a molecular weight of about 100 to 800 and having the following structure is more preferable.

<< Acid generator >>
The composition of the present invention can also contain an acid generator. The acid generator may be a photoacid generator or a thermal acid generator, but a thermal acid generator is preferred. When a thermal acid generator is used, the heat resistance of the cured film tends to be further improved.
The thermal acid generator refers to an acid generator that generates an acid when heated at 100 to 250 ° C. at 101.25 hPa. The acid generated is preferably an acid having a pKa of 5 or less. Specific examples of the acid generated include sulfonic acid, carboxylic acid, phosphoric acid and the like, and sulfonic acid is more preferable.
As the photoacid generator, the description in paragraphs 0103 to 0113 of JP-A-2006-259002 can be referred to, and the contents thereof are incorporated in the present specification.
Thermal acid generators include ionic compounds (onium salts) and nonionic compounds.
As the ionic compound (onium salt), those containing no heavy metal or halogen ion are preferable, and onium salts of sulfonic acid are preferable.
Specific examples of the ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethyl. Sulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, these Examples thereof include methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, para-toluenesulfonate, hexafluorophosphonate and the like.

<< Photosensitizer >>
The composition of the present invention may contain a photosensitizer. As the sensitizer, Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The photosensitizer is preferably contained in an amount of 50 to 200% by mass with respect to the photopolymerization initiator.

<< Curing accelerator >>
The composition of the present invention can contain a compound that functions as a curing accelerator.
For example, at least one compound selected from the group consisting of aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds, thiol compounds, blocked isocyanate compounds, and imidazole ring-containing compounds can be used. .
When the composition of this invention contains a hardening accelerator, the low temperature hardening of a composition can be implement | achieved more effectively. In addition, the storage stability of the composition can be further improved.
Examples of commercially available curing accelerators include Karenz MT series such as Karenz MTBD-1 (manufactured by Showa Denko KK).
In this invention, a hardening accelerator can be used individually or in mixture of 2 or more types. The content of the curing accelerator is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.

<< Chain transfer agent >>
The composition of the present invention may contain a chain transfer agent. Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N -Heterocycles such as phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The content of the chain transfer agent is preferably 0.01 to 15% by mass with respect to the total solid content of the composition of the present invention, from the viewpoint of reducing sensitivity variation, and is preferably 0.1 to 10% by mass. Is more preferable, and 0.5 to 5% by mass is particularly preferable.

<< Polymerization inhibitor >>
The composition of the present invention may contain a polymerization inhibitor. A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the composition by light or heat. ) And the like, inactivate the polymerization initiating species, and play a role of suppressing unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A can be used. Of these, para-methoxyphenol is preferably used as the polymerization inhibitor.
The content of the polymerization inhibitor in the composition of the present invention is preferably 0.0001 to 5% by mass, more preferably 0.001 to 5% by mass, and more preferably 0.001 to 1% with respect to the total mass of the polymerizable compound. Mass is particularly preferred.

<< Adhesion improver >>
The composition of the present invention may contain an adhesion improving agent. The adhesion improver is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
0.1-20 mass% is preferable with respect to the total solid of a composition, and, as for content of the adhesion improving agent in the composition of this invention, 0.2-5 mass% is more preferable.

<< Development accelerator >>
In the case where the alkali solubility in the non-exposed area is promoted to further improve the developability of the coloring composition, a development accelerator can be added. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
Various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the colored composition of the present invention as necessary. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
In the coloring composition of this invention, the light stabilizer as described in Paragraph [0078] of Unexamined-Japanese-Patent No. 2004-295116 and the thermal-polymerization inhibitor as described in Paragraph [0081] of the same gazette can be contained.

<Method for preparing colored composition>
The coloring composition of the present invention can be prepared by mixing the above-described components and optional components as necessary.
In preparing the colored composition, the components constituting the colored composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

  Since the colored composition of the present invention can form a cured film excellent in hue and contrast, for forming a colored layer (for forming colored pixels) such as a color filter used in an image display device or a solid-state imaging device, Moreover, it can use suitably as preparation uses, such as printing ink, inkjet ink, and a coating material.

<Method for producing cured film, color filter, color filter>
The cured film of the present invention is formed by curing the colored composition of the present invention. Such a cured film is preferably used for a color filter.

The color filter of the present invention may be formed by any method as long as it can form a colored region (colored pattern) cured by applying the colored composition of the present invention on a support. Preferably, it is produced using the coloring composition of the present invention.
Moreover, when manufacturing the color filter for solid-state image sensors using the coloring composition of this invention, the manufacturing method described in Paragraph 0359-0371 of Unexamined-Japanese-Patent No. 2011-252065 can also be employ | adopted. .

  The method for producing a color filter of the present invention includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern, and a colored composition layer. And a step of developing and removing the unexposed portion to form a colored pattern. Furthermore, you may provide the process (prebaking process) of baking a colored composition layer, and the process (post-baking process) of baking the developed coloring pattern as needed.

<< Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer is formed by applying the colored composition of the present invention on the support.

As the support, for example, non-alkali glass, sodium glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached to a liquid crystal display element or the like, a solid-state imaging element, or the like is used. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  As a method of applying the coloring composition, coating is preferable, and coating is preferably performed by a method such as spin coating, slit coating, cast coating, roll coating, bar coating, and ink jet.

  The colored composition layer formed on the support is preferably dried (prebaked). Pre-baking can be performed at 70 ° C to 130 ° C for 0.5 to 15 minutes using a hot plate, oven, or the like.

  The thickness of the colored composition layer formed from the colored composition is appropriately selected according to the purpose. In the case of a color filter for an image display device, a range of 0.2 to 5.0 μm is preferable, a range of 1.0 to 4.0 μm is more preferable, and a range of 1.5 to 3.5 μm is most preferable. Moreover, in the case of the color filter for solid-state image sensors, the range of 0.2-5.0 micrometers is preferable, The range of 0.3-2.5 micrometers is more preferable, The range of 0.3-1.5 micrometers is the most preferable. In addition, the thickness of a coloring composition layer is a film thickness after prebaking.

<< Exposure Step >>
Subsequently, in the method for producing a color filter of the present invention, the film (colored composition layer) made of the colored composition formed on the support as described above is exposed through, for example, a photomask. . As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

Exposure Step Using Laser Light Source In an exposure method using a laser light source, it is preferable to use an ultraviolet laser as the light source. The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, and more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. Specifically, the third harmonic (355 nm) of an Nd: YAG (yttrium, aluminum, garnet) laser, which is a relatively inexpensive solid laser with a large output, and the XeCl (308 nm), XeF (353 nm) of an excimer laser. Can be suitably used. The pattern exposure is preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm ² is more preferable.

  There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), DF2200G (Dainippon Screen) can be used. It is. Further, devices other than those described above are also preferably used.

<< Step of forming colored pattern >>
Subsequently, development is performed with a developer on the colored composition layer after exposure. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored composition layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used.
When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

In the method for producing a color filter of the present invention, in particular, post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored composition.
Further, it is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

  By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.

  In the method for producing a color filter of the present invention, in particular, post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored composition.

The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having pixels of a plurality of hues, the above steps may be repeated according to a desired number of colors.
It should be noted that the post-exposure and / or post-bake treatment may be performed each time the formation, exposure, and development of a single-color coloring composition layer is completed (for each color), or all colors having a desired number of colors may be used. After the formation, exposure, and development of the composition layer are completed, the post-exposure and / or post-bake treatment may be performed collectively.

Moreover, the coloring composition of this invention is applicable also to the manufacturing method of the color filter containing a dry etching process. As an example of such a production method, a step of forming a colored layer using the colored composition of the present invention,
Manufacturing comprising a step of forming a photoresist layer on a colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask A method is mentioned.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast because the colored composition of the present invention is used.
The color filter of the present invention can be used for an image display device or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image having excellent spectral characteristics and contrast while achieving a good hue.

<Image display device>
The image display device of the present invention comprises the color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. It is particularly suitable for liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics. In particular, the color filter of the present invention includes at least a red color filter, a blue color filter, and a green color filter. Can display a high-quality image with excellent display characteristics.

  For the definition of the image display device and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.

  When the color filter of the present invention is used in an image display device, a high contrast can be realized when combined with a conventionally known three-wavelength cold-cathode tube, but further, red, green and blue light-emitting diode light sources (RGB-LED). ) As a backlight, an image display device having high luminance and high color purity and good color reproducibility can be provided.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

On a support, transfer electrodes made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) are provided. A nitride film formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. The device has a device protective film made of silicone or the like, and has the color filter for a solid-state imaging device of the present invention on the device protective film.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light condensing means on the color filter Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis Example 1>
(Synthesis of TAM001-A)
4,4'-dichlorobenzophenone (Tokyo Chemical Industry Co., Ltd.) 12.5 g, 2,4,6-trimethylaniline (Tokyo Chemical Industry Co., Ltd.) 15.0 g, tert-butoxy sodium (tBuONa) 14.4 g, 150 mL of toluene was placed in a flask and stirred at room temperature under a nitrogen atmosphere. To this, 56 mg of palladium acetate (Pd (OAc) ₂ ) (manufactured by Wako Pure Chemical Industries, Ltd.) and 266 mg of tri-tert-butylphosphonium tetrafluoroborate (tBu ₃ P) (manufactured by Wako Pure Chemical Industries, Ltd.) were added. After that, the mixture was stirred for 4 hours under heating and refluxing conditions. After cooling, 200 mL of ethyl acetate and 200 mL of water were added, and the precipitated crystals were collected by filtration. The crystals were heated and washed with 100 mL of ethyl acetate to obtain 8.0 g of TAM001-A crystals.
(Synthesis of TAM001-B)
50 g of 1-aminonaphthalene, 38 g of 1,2-epoxycyclohexane, and 150 mL of 1,3-hexafluoro-2-propanol were added to the flask, and the mixture was stirred for 5 hours under reflux with heating. After cooling to room temperature, the solvent was concentrated. Subsequently, the suspension was heated and washed with 200 mL of hexane. The obtained crystals were filtered and further washed with isopropyl alcohol to obtain TAM001-B (56 g).
(Synthesis of TAM001 chloro salt)
5 g of TAM001-A, 4 g of TAM001-B, 50 ml of toluene, and ₃ g of phosphorus oxychloride (POCl ₃ ) were added to the flask and reacted at 90 ° C. for 6 hours. After cooling the reaction solution to room temperature, 50 ml of hexane was added to separate the organic solvent and the dye. The crude dye was suspended and filtered with 50 ml of ethyl acetate to obtain 7 g of TAM001 chloro salt.
(Preparation of Dawson type phosphotungstic acid solution)
Sodium tungstate dihydrate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 45.5 parts by mass, 80.8% by mass of phosphoric acid (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 60.8 parts by mass of 232.2 parts by mass of water And heated to reflux for 7 hours. After adding 4 drops of bromine water, it was cooled to prepare a Dawson type phosphotungstic acid solution. When this solution was analyzed by ³¹ P-NMR (nuclear magnetic resonance), only α-form and β-form Dawson-type phosphotungstate ions were detected, and it was confirmed that the mixture was a mixture of two types of heteropolyacids.
(Synthesis of colorant PB1)
5 parts by mass of TAM001 chloro salt, 200 parts by mass of water, and 100 parts by mass of methanol were put into a flask and stirred at 40 ° C. 16 parts by mass of the Dawson type phosphotungstic acid solution prepared above (about 5 parts by mass as Dawson type phosphotungstic acid) was added, and the mixture was stirred at 40 ° C. for 1 hour. Subsequently, the internal temperature was raised to 80 ° C., and further stirred at this temperature for 1 hour. After cooling, the mixture was filtered, washed with 1000 parts by mass of water three times, and then dried at 90 ° C. to obtain 10 parts by mass of a solid (black blue solid). The obtained solid was pulverized with a commercially available juicer to obtain a colorant PB1. In this colorant PB1, the cation portion had the following TAM001 structure and the anion portion was a phosphotungstate anion.

<Synthesis Example 2>
(Synthesis of TAM002-A)
To a mixed solution of TAM001-A 2.6 g, sodium hydride (oil mixture, 60% by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methylpyrrolidone (NMP) 25 mL, 1-methyl iodide (MeI) (Kanto) 10 g of Chemical Co.) was added dropwise at room temperature. The solution after dropping was stirred at 40 ° C. for 2 hours. After cooling the reaction solution to room temperature, 100 mL of water was added. After the pH of the solution was adjusted to 6-7 with hydrochloric acid, the precipitated crude crystals were filtered. The crude crystals were suspended and washed with n-hexane to obtain 1.7 g of TAM002-A crystals.
(Synthesis of TAM002 chloro salt body)
A TAM002 chloro salt was synthesized in the same manner as the synthesis of the TAM001 chloro salt except that TAM002-A and N-phenylnaphthylamine (Tokyo Chemical Industry Co., Ltd.) were used.
(Synthesis of colorant PB2)
TAM001 Chloro salt is replaced with TMA002 Chloro salt in the same manner as the synthesis of colorant PB1, except that 5 parts by mass of TMA002 chloro salt is used. Colorant PB2 was obtained.

<Synthesis Example 3>
(Synthesis of colorant PB3)
Instead of using TAM001 chloro salt and Dawson phosphotungstic acid solution, 5 parts by weight of TAM002 chloro salt and 5 parts by weight of Keggin silicotungstic acid hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) By a method similar to the synthesis of the colorant PB1, a colorant PB3 having a cation portion of the following formula TAM002 and an anion portion of silicotungstate anion was obtained.

<Synthesis Example 4>
(Synthesis of colorant PB4)
Instead of TAM001 chloro salt and Dawson phosphotungstic acid solution, colored except that 5 parts by weight of TAM002 chloro salt and 5 parts by weight of sodium phosphomolybdate hydrate (manufactured by Nippon Shin Metal Co., Ltd.) were used. In the same manner as in the synthesis of the agent PB1, a colorant PB4 having a cation moiety of the following formula TAM002 and an anion moiety of a phosphomolybdate anion was obtained.

<Synthesis Example 5>
(Synthesis of TAM003 chloro salt)
A TAM003 chloro salt was synthesized in the same manner as the synthesis of the TAM001 chloro salt except that TAM002-A and N-ethylnaphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were used.
(Synthesis of colorant PB5)
TAM001 Chloro salt is replaced with TAM003 Chloro salt in the same manner as the synthesis of colorant PB1, except that 5 parts by mass of TAM003 chloro salt is used. Agent PB5 was obtained.

<Synthesis Example 6>
(Synthesis of TAM004 chloro salt)
TAM004 chloro salt was synthesized in the same manner as TAM001 chloro salt except that TAM002-A and TAM001-B were used.
(Synthesis of colorant PB6)
TAM001 Chloro salt is used in the same manner as the synthesis of the colorant PB1, except that 5 parts by mass of TAM004 chloro salt is used, and the cation moiety is TAM00 and the anion moiety is a phosphotungstic anion. Agent PB6 was obtained.

(Synthesis Example 7)
Synthesis was performed in the same manner as in Synthesis Example 1 except that 2,4,6-trimethylaniline used in the synthesis of TAM001 in Example 1 was changed to aniline. A colorant PB7 in which is a phosphotungstate anion was obtained.

(Colorant R-1)
C. I. Pigment Blue 1 (manufactured by BASF) was used as colorant R-1.

(Coloring agent R-2)
According to the method described in Example 1 (paragraph number 0066) of JP2011-186043 A, a colorant R-2 in which the cation portion is represented by the following formula B7 and the anion portion is a phosphotungstate anion was synthesized.

(Coloring agent R-3)
According to the method described in Example 2 (paragraph number 0041) of WO2010-123071, a coloring agent R-3 having a cation moiety represented by the following formula B7 and an anion moiety of bistrifluoromethylsulfonylimide was synthesized.

(Cation structure)

(Examples 1-7, Comparative Examples 1-2)
[Preparation of colorant dispersion]
1.80 parts by mass of the colorant described in Table 2 below, 2.10 parts by mass of Disperbyk-2164 manufactured by BYK (BYK), 1.10 parts by mass of propylene glycol monomethyl ether acetate 1, and a diameter of 0.3 to 0 4 mm Sepul beads were placed in a polyethylene container and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a colorant dispersion.
[Preparation of colored composition]
Components in the following composition were mixed to prepare a colored composition.
Colorant dispersion: 10.0 parts by mass Polymerizable compound (T-1): 6.5 parts by mass Alkali-soluble resin (U-1): 8.5 parts by mass Photopolymerization Initiator (V-3) ... 1.0 parts by mass, solvent (X-1) ... 40.0 parts by mass, solvent (X-2) ... 12.0 parts by mass, Surfactant (Z-1): 0.006 parts by mass

(Comparative Example 3)
A colored composition of Comparative Example 3 was prepared in the same manner as described above except that 1.5 parts by mass of the colorant R-3 was used instead of the colorant dispersion.

Polymerizable compound (T-1): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Alkali-soluble resin (U-1): benzyl methacrylate / methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) acid value (100 mg KOH / g))
Photopolymerization initiator (V-3): an oxime compound having the following structure
Solvent (X-1): Propylene glycol monomethyl ether acetate Solvent (X-2): Ethyl 3-ethoxypropionate Surfactant (Z-1): The following mixture (Mw = 14000)

<Preparation of colored layer A>
The colored composition obtained above is applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) by a spin coating method, and then dried at room temperature for 30 minutes to volatilize volatile components and thereby form a colored layer. Got. This colored layer was irradiated with i-rays (wavelength 365 nm) exposed on the entire surface without using a photomask to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² . Next, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. , Dried with spray. The dried film was baked in a clean oven at 230 ° C. for 20 minutes to obtain a colored layer A.

<Heat resistance>
The transmission spectrum of the colored layer A obtained above and the transmission spectrum when the colored layer A was additionally baked at 230 ° C. for 120 minutes were measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The color difference (ΔEab) was calculated. A smaller ΔEab value indicates better heat resistance.
The ΔEab value is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by New Color Science Handbook (Showa 60) p.266). .
ΔEab = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^1/2

<Solvent resistance (color difference)>
The colored layer A obtained above is immersed in NMP (N-methylpyrrolidone) at 25 ° C. for 10 minutes, and the transmission spectrum before and after the immersion is measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). And the color difference (ΔEab) was calculated. The color difference was calculated from the transmission spectrum of the colored layer A before and after being immersed in NMP. A smaller ΔEab value indicates better solvent resistance.

<Voltage holding ratio>
On a glass substrate (trade name: 1737 manufactured by Corning) with an ITO (Indium Tin Oxide) electrode, the colored composition was applied to a thickness of 2.0 μm after drying, and dried in an oven at 90 ° C. for 60 seconds ( Pre-baked). Then, exposure is performed at 100 mJ / cm ² without using a mask (illuminance is 20 mW / cm ² ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is used. The coating film was developed at 25 ° C., washed with water and dried, and then heat-treated (post-baked) for 30 minutes in an oven at 230 ° C. to form a cured film. Next, the substrate on which this cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then Merck liquid crystal MJ971118 (trade name) between the substrates. Was injected to prepare a liquid crystal cell.
Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C. for 48 hours, the voltage holding ratio of the liquid crystal cell was measured using the liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica under the following measurement conditions. It measured and evaluated by the score shown to the following reference | standard. The higher the score, the better the voltage holding ratio.
Measurement conditions / Distance between electrodes: 5 μm to 15 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
-Applied voltage pulse width: 16.67 msec
Voltage holding ratio: potential difference of liquid crystal cell after 16.7 milliseconds / value applied for voltage applied at 0 milliseconds 90% or more: 5
85% or more and less than 90%: 4
80% or more and less than 85%: 3
75% or more and less than 80%: 2
Less than 75%: 1

<Light resistance>
Transmission spectrum of colored layer A obtained above, and transmission spectrum of colored layer A after irradiation of colored layer A with a xenon fade meter (XL-75 manufactured by Suga Test Instruments Co., Ltd.) for illuminance of 390 W / m ² for 48 hours. Was measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), and the color difference (ΔEab) was calculated. A smaller ΔEab value indicates better light resistance.

As shown in the above table, the examples were excellent in heat resistance. Further, it was excellent in light resistance, voltage holding ratio, and solvent resistance.
On the other hand, the comparative example was inferior in heat resistance to the examples.

Claims (13)

A coloring composition comprising a colorant and a resin,
The colorant includes a cation represented by the following general formula (2) ,
An anion containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom, and an oxygen atom;
Coloring composition;
In General Formula (2), R ^1a and R ^2a each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R ^3a represents an alkyl group having 1 to 6 carbon atoms or a carbon number having 6 to 9 carbon atoms. R ^{7 to} R ¹² each independently represents a methyl group, an ethyl group or an isopropyl group. The coloring composition according to claim 1 , wherein R ^1a and R ^{2a in} the general formula (2) are methyl groups. The anion is an anion of a heteropolyacid containing at least one selected from a tungsten atom and a molybdenum atom, and an anion of an isopolyacid containing at least one selected from a tungsten atom and a molybdenum atom. The coloring composition according to claim 1 or 2 . The coloring composition according to any one of claims 1 to 3 , wherein the anion is at least one selected from a phosphotungstate anion, a silicotungstate anion, and a phosphomolybdate anion. Furthermore, the coloring composition of any one of Claims 1-4 containing a polymeric compound. The cured film formed by hardening | curing the coloring composition of any one of Claims 1-5 . A color filter having the cured film according to claim 6 . A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 5 , a step of exposing the colored composition layer in a pattern, and the colored composition And a step of developing and removing an unexposed portion of the physical layer to form a colored pattern. A solid-state imaging device having the color filter according to claim 7 . An image display device comprising the color filter according to claim 7 . 12. The image display device according to claim 11, wherein the image display device includes at least a red color filter, a blue color filter, and a green color filter, and the blue color filter is the color filter according to claim 7. The image display device described. A cation represented by the following general formula (2) ;
An anion containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom, and an oxygen atom;
Having a colorant;
In General Formula (2), R ^1a and R ^2a each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R ^3a represents an alkyl group having 1 to 6 carbon atoms or a carbon number having 6 to 9 carbon atoms. R ^{7 to} R ¹² each independently represents a methyl group, an ethyl group or an isopropyl group. A compound having a cation represented by the following general formula ( 2 );
A method for producing a colorant, wherein a compound containing at least one selected from a tungsten atom, a molybdenum atom, a silicon atom and a phosphorus atom and an oxygen atom is reacted in a solvent;
In General Formula (2), R ^1a and R ^2a each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R ^3a represents an alkyl group having 1 to 6 carbon atoms or a carbon number having 6 to 9 carbon atoms. R ^{7 to} R ¹² each independently represents a methyl group, an ethyl group or an isopropyl group.