JP6307164B2 - Pigment dispersion, method for producing pigment dispersion, colored composition, cured film, color filter, method for producing color filter, solid-state imaging device, image display device and composition - Google Patents

Description

  The present invention relates to a pigment dispersion, a method for producing a pigment dispersion, 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, and a composition.

  In recent years, the demand for solid-state imaging devices such as CCD (Charge Coupled Device) image sensors has greatly increased due to the spread of digital cameras, camera-equipped mobile phones and the like. Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for higher sensitivity and miniaturization. Such a color filter normally has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and plays a role of separating transmitted light into the three primary colors.

Patent Document 1 discloses a pigment dispersion containing a pigment dispersant having a dye skeleton, a pigment, and a solvent, wherein the difference between the maximum absorption wavelength of the pigment dispersant having the dye skeleton and the maximum absorption wavelength of the pigment is 200 nm or less. Is described.
Patent Document 2 discloses an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxy group A polymer compound having a monovalent organic group containing at least one site selected from a silyl group, an epoxy group, an isocyanate group, and a hydroxyl group is described.

JP 2011-1118060 A JP 2007-277514 A

Although coloring compositions using various dispersants have been studied, in recent years, further improvements in color loss have been demanded in coloring compositions used for color filters and the like.
The present invention has been made in view of such a situation, and an object thereof is to provide a pigment dispersion for providing a color filter having high color loss resistance and a coloring composition using the pigment dispersion. . Moreover, it aims at providing the manufacturing method of a pigment dispersion liquid, a cured film, a color filter, the manufacturing method of a color filter, a solid-state image sensor, an image display apparatus, and a composition.

As a result of detailed studies, the present inventors have found that the above problems can be solved by using a dispersant having a predetermined dye structure, and have completed the present invention.
Specifically, the above problem has been solved by the following means <1>, <17> or <18>, preferably <2> to <16>.
<1> A pigment dispersion containing a dispersant having a dye structure, a pigment, and a solvent,
The dispersant having a dye structure has a dye structure selected from a triarylmethane dye, a xanthene dye, a cyanine dye and a squarylium dye;
The dispersant having a dye structure is a dye multimer having two or more dye structures in the same molecule, and the specific absorbance represented by the following formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm is 5 or more. Pigment dispersions;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of a dispersant having a dye structure in a solution, the unit of which is expressed in mg / ml. <2> The dye structure of the dispersant having a dye structure contains an anion moiety, and the anion moiety is a sulfonate anion, a carboxylate anion, a tetraarylborate anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , The pigment dispersion according to <1>, which is at least one selected from the group consisting of a group including the structure represented by (A1) and a group including a structure represented by the following general formula (A2);
General formula (A1)
In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.
General formula (A2)
In general formula (A2), R ³ represents —SO ₂ — or —CO—; R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN.
<3> The pigment dispersion according to <1> or <2>, wherein the pigment is contained in an amount of 80 to 150 parts by mass with respect to 100 parts by mass of the dispersant having a dye structure.
<4> The pigment dispersion according to any one of <1> to <3>, wherein the dispersant having a dye structure has a weight average molecular weight of 3,000 to 50,000.
<5> The pigment dispersion according to any one of <1> to <4>, wherein the acid value of the dispersant having a dye structure is 27 mgKOH / g or more and less than 200 mgKOH / g.
<6> A colored composition comprising the pigment dispersion according to any one of <1> to <5> and a curable compound.
<7> The colored composition according to <6>, further containing a photopolymerization initiator.
<8> The pigment according to <6> or <7>, wherein the pigment is 25% by mass or more of the total solid content of the coloring composition, and the total of the dispersant having a dye structure and the pigment is 60% by mass or more. Coloring composition.
<9> The colored composition according to any one of <6> to <8>, which is for a color filter.
<10> A cured film obtained by curing the colored composition according to any one of <6> to <9>.
<11> A color filter using the colored composition according to any one of <6> to <9>.
<12> A step of applying the colored composition according to any one of <6> to <9> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, And a step of developing and removing an unexposed portion of the exposed colored composition layer to form a colored pattern.
<13> A step of applying the colored composition according to any one of <6> to <9> on a support to form a colored composition layer and curing to form a colored layer;
Forming a photoresist layer on the colored layer;
A method for producing a color filter, comprising: a step of patterning a photoresist layer by exposing and developing the photoresist layer to obtain a resist pattern; and a step of dry etching a colored layer using the resist pattern as an etching mask.
<14> A solid-state imaging device having the color filter according to <11> or the color filter manufactured by the method for manufacturing a color filter according to <12> or <13>.
<15> An image display device having the color filter according to <11> or the color filter manufactured by the method for manufacturing a color filter according to <12> or <13>.
<16> including a step of dispersing the pigment in the presence of a dispersant having a dye structure,
The dispersant having a dye structure has a dye structure selected from a triarylmethane dye, a xanthene dye, a cyanine dye and a squarylium dye;
The dispersant having a dye structure is a dye multimer having two or more dye structures in the same molecule, and the specific absorbance represented by the following formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm is 5 or more. A method for producing a pigment dispersion;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of a dispersant having a dye structure in a solution, the unit of which is expressed in mg / ml. <17> A composition comprising a resin represented by the following general formula (1), a pigment and a solvent,
The resin has a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes;
A composition in which the resin has a specific absorbance of 5 or more represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the resin having the dye structure in the solution, expressed in mg / ml; the general formula (1)
_{^{(D-R 2) n -R}} 1 - (L 1 -P) m ··· (1)
In general formula (1), R ¹ represents a (m + n) -valent linking group,
P represents a monovalent substituent having a repeating unit;
D represents the dye structure;
R ² and L ¹ each independently represents a single bond or a divalent linking group,
m represents an integer of 1 to 13,
when m is 1, P represents a monovalent substituent having two or more repeating units;
When m is 2 or more, the plurality of Ps may be different from each other, the average value of the number of repeating units constituting the plurality of Ps is 2 or more,
n represents an integer of 2 to 14,
when n is 2 or more, the plurality of D may be different from each other;
m + n represents an integer of 2 to 15.
<18> A composition containing 80 to 150 parts by mass of a pigment and a solvent with respect to 100 parts by mass of a resin including a repeating unit represented by the following general formula (A)
The resin has a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes;
A composition in which the resin has a specific absorbance of 5 or more represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the resin having a dye structure in the solution, the unit of which is expressed in mg / ml; the repeating unit represented by the general formula (A);
In general formula (A), X ₁ represents a linking group formed by polymerization, and L ₁ represents a single bond or a divalent linking group. DyeI represents a dye structure.

  According to the present invention, it is possible to provide a pigment dispersion for providing a color filter having high color loss resistance, and a coloring composition using the pigment dispersion. In addition, it is possible to provide a method for producing a pigment dispersion, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, and a composition.

Hereinafter, the contents of the present invention will be described in detail.
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 as well as 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).

  As used herein, “active light” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV (Extreme ultraviolet) light), X-rays, electron beams, and the like. means. 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 the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
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. The solid content and concentration in the present invention refer to those at 25 ° C.

  In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl, and “(meth) acryloyl” "" Represents both and / or acryloyl and methacryloyl.

  In the present specification, “monomer” and “monomer” are synonymous. 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 means 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, and Ph represents a phenyl 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. .

  In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC (Gel Permeation Chromatography) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column. ) Can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

<Pigment dispersion>
The pigment dispersion of the present invention is a pigment dispersion containing a dispersant having a dye structure, a pigment, and a solvent, and the dispersant having a dye structure is composed of a triarylmethane dye, a xanthene dye, a cyanine dye, and a squarylium dye. The dispersant having the selected dye structure and having the dye structure is a dye multimer having two or more dye structures in the same molecule, and is represented by the following formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm. Specific absorbance is 5 or more.
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of a dispersant having a dye structure in a solution, the unit of which is expressed in mg / ml.
Here, the cell length refers to the length of the cell used when measuring the absorbance.
The “dispersant having a dye structure” in the present invention is a dye multimer having two or more dye structures in the same molecule. The reason why the dye multimer is effective as a dispersant is not clear, but it is considered that two or more dye structure sites of the dye multimer are adsorbed to the pigment, thereby helping the dispersion progress in the pigment dispersion process.
The dispersant having a dye structure has two or more dye structures in the same molecule, preferably 2 to 100, more preferably 2 to 50, and still more preferably 2 to 20.

By adopting the above configuration, color loss can be suppressed. The reason why such an effect is obtained is not yet clear, but by using the above dispersant in combination with the pigment, the pigment is easily adsorbed on the dye portion of the dispersant, and color loss can be suppressed.
Moreover, it becomes possible to contain more said dispersing agent and a pigment, and the light resistance when it is set as a cured film can be improved more.
Furthermore, by setting it as the said structure, the image development residue when it is set as a coloring composition can be suppressed more, and color nonuniformity (zara) can be suppressed more.

<< Dispersant having a dye structure >>
<<< Dye structure >>>
The dispersant having a dye structure has a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes.
Of these dye structures, triarylmethane dyes and xanthene dyes are more preferable.
Hereinafter, the dye structure preferably used in the present invention will be described in detail.

<<<<< Triarylmethane Dye >>>>
One embodiment of the dye structure is one having a partial structure derived from a triarylmethane dye. Examples of the triarylmethane dye include a structure represented by the following formula (TP).

Formula (TP)

In the formula (TP), Rtp ^{1 to} Rtp ⁴ each independently represents a hydrogen atom, an alkyl group, or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b, and c represent an integer of 0-4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked to each other to form a ring. X ⁻ represents an anion structure. When X ⁻ is not present, at least one of Rtp ^{1 to} Rtp ⁷ contains an anion.
In the formula (TP), via RTP ^{1 to} Rtp ¹⁰ , another part of the dispersant (preferably R ² in the general formula (1) or L ^{1 in the} general formula (A) described later) It is preferable that it binds to other part of the dispersant via Rtp ⁵ .

Rtp ^{1 to} Rtp ⁶ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp ⁵ is preferably a hydrogen atom or NRtp ⁹ Rtp ¹⁰ , particularly preferably NRtp ⁹ Rtp ¹⁰ . Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. As the substituent represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ , the substituents mentioned in the section of Substituent Group A described later can be used, and in particular, a linear or branched alkyl group having 1 to 5 carbon atoms, A C1-C5 alkenyl group, a C6-C15 aryl group, a carboxyl group, or a sulfo group is preferable, a C1-C5 linear or branched alkyl group, a C1-C5 alkenyl group, phenyl A group or a carboxyl group is more preferable. In particular, Rtp ⁶ and Rtp ⁸ are preferably an alkyl group having 1 to 5 carbon atoms, and Rtp ⁷ is preferably an alkenyl group (especially a phenyl group in which two adjacent alkenyl groups are linked), a phenyl group or a carboxyl group. .
a, b or c each independently represents an integer of 0 to 4; In particular, a and c are each preferably 0 or 1, more preferably 0. b is preferably an integer of 0 to 2, and more preferably 0 or 2.

Specific examples of the compound represented by the formula (TP) are shown below, but the present invention is not limited thereto. In the following specific examples, X ⁻ represents an anion.

<<<<< Xanthene Dye >>>>
As the xanthene dye, those having a partial structure derived from a xanthene compound represented by the following formula (J) as the dye structure are exemplified.

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, m Represents an integer of 0 to 5. X ⁻ represents an anion site. When X ⁻ is not present, at least one of R ^{81 to} R ⁸⁵ contains an anion. In the formula (J), through one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ , another part of the dispersant (preferably R ^{2 of} the general formula (1) described later or the general formula ( It is preferably bonded to L ¹ ) of A), and more preferably bonded to another part of the dispersant via R ⁸⁵ .

The substituents that can be taken by R ^{81 to} R ⁸⁵ in Formula (J) are the same as the substituents mentioned in the section of Substituent Group A described later.

R ⁸¹ and R ^{82 in} formula (J), R ⁸³ and R ⁸⁴ , and R ^{85 in} the case where m is 2 or more are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered saturated ring. Or a 5-membered, 6-membered or 7-membered unsaturated ring. 5-membered to be formed, ring 6- or 7 members, in the case of further substitutable groups may be substituted with substituents described in R ⁸¹ to R ^85, 2 or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
In the above formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ^{85 in} the case where m is 2 or more are each independently bonded to each other, and have no substituent. 5-membered and 7-membered saturated ring or 5-membered, 6-membered and 7-membered unsaturated ring, when forming 5-membered, 7-membered saturated ring or 5-membered, 6-membered and 7-membered Examples of the unsaturated ring include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring and pyridine ring. , A pyrazine ring and a pyridazine ring, preferably a benzene ring and a pyridine ring.

In particular, R ⁸² and R ⁸³ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are preferably a substituted or unsubstituted alkyl group or a phenyl group. R ⁸⁵ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group or an amide group, and a sulfo group, a sulfonamide group, a carboxyl group, More preferred is an amide group. R ⁸⁵ is preferably bonded to the adjacent part of carbon linked to the xanthene ring. The substituent that the phenyl group of R ⁸¹ and R ⁸⁴ has is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.

  The compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, the methods described in Tetrahedron Letters, 2003, vol. 44, No. 23, pages 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pages 3097-3106, etc. Can be applied.

When X ⁻ represents an anion, the description in the case where the anion site described later is a different molecule can be considered. In addition, when X ⁻ is not present and at least one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ contains an anion, the description of the case where the anion portion is in the same repeating unit can be referred to.

Hereinafter, specific modes (first mode and second mode) of the compound represented by formula (J) will be described.
(First embodiment of compound represented by formula (J))
In the compound represented by the formula (J), one of R ⁸¹ and R ⁸³ is a group represented by the following general formula (2), the other of R ⁸¹ and R ⁸³ is a hydrogen atom, and the following general formula (2) Or an aryl group other than the group represented by the general formula (2) or an alkyl group. R ⁸² and R ⁸⁴ may each independently represent a hydrogen atom, an alkyl group, or an aryl group.
General formula (2)

In General Formula (2), R ¹ and R ² each independently represents an alkyl group having 3 or more carbon atoms, an aryl group, or a heterocyclic group, and X ^{1 to} X ³ each independently represent a hydrogen atom. Alternatively, it represents a monovalent substituent. The dye compound represented by the general formula (1) has an anion site inside and / or outside the molecule.

In general formula (1), one of R ⁸¹ and R ⁸³ is a group represented by general formula (2), and the other of R ⁸¹ and R ⁸³ is a hydrogen atom, represented by the following general formula (2). An aryl group other than the group represented by formula (2) or an alkyl group, and an aryl group other than the group represented by formula (2) or the group represented by formula (2). May be. Further, both of R ⁸¹ and R ⁸³ may be a group represented by the general formula (2). When both R ⁸¹ and R ⁸³ are groups represented by the general formula (2), the groups represented by the two general formulas (2) may be the same or different.

In general formula (2), R ¹ and R ² each independently represents an alkyl group having 3 or more carbon atoms, an aryl group, or a heterocyclic group, and a secondary or tertiary alkyl group having 3 to 12 carbon atoms. Or an isopropyl group.
Specifically, the alkyl group having 3 or more carbon atoms may be linear, branched or cyclic, may have 3 to 24 carbon atoms, may have 3 to 18 carbon atoms, The number 3-12 may be sufficient. Specifically, for example, propyl group, isopropyl group, butyl group (for example, t-butyl group), pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, And cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, It may be a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a propyl group, an isopropyl group, a butyl group (t-butyl group), a pentyl group, a hexyl group, a heptyl group, an octyl group, or a 2-ethylhexyl group. Isopropyl group, t-butyl group, 2-ethylhexene It may be a le group.
The aryl group includes a substituted or unsubstituted aryl group. The substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent are the same as those of the substituent group A described later.
The heterocycle of the heterocycle group may be a 5-membered or 6-membered ring, and they may be further condensed or not condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. For example, pyridine ring, pyrazine ring, pyridazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring , Imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, thiadiazole ring, isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine Ring, piperazine ring, imidazolidine ring, thiazoline ring and the like. Among them, it may be an aromatic heterocycle, such as a pyridine ring, pyrazine ring, pyridazine ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, benzine. Examples include isothiazole ring and thiadiazole ring, and may be pyrazole ring, imidazole ring, benzoxazole ring, thiadiazole ring, pyrazole ring, thiadiazole ring (1,3,4-thiadiazole ring, 1,2,4-thiadiazole) Ring). They may have a substituent, and examples of the substituent are the same as those of the aryl group described later.
R ¹ and R ² may be an alkyl group having 3 or more carbon atoms, or an alkyl group having 3 to 12 carbon atoms.

In General Formula (2), X ^{1 to} X ³ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent include the substituent group A described later. X ^{1 to} X ³ may be a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, an alkylthio group, a sulfonamide group, or a sulfamoyl group.

  A phenyl group is mentioned as aryl groups other than the group represented by General formula (2). The phenyl group may or may not have a substituent. Examples of the substituent include substituent group A described later, and may be an alkyl group or an aryl group.

R ⁸² and R ⁸⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and the alkyl group and the aryl group may or may not have a substituent.
The substituted or unsubstituted alkyl group may be an alkyl group having 1 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent group A mentioned later is mentioned. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (t-butyl group), an n-octyl group, and a 2-ethylhexyl group.
The substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent are the same as those of the substituent group A described later.
R ⁸² and R ⁸⁴ may be a hydrogen atom or an alkyl group, and may be a hydrogen atom.

(Second embodiment of compound represented by formula (J))
In the compound represented by the formula (J), R ⁸¹ and R ⁸³ may each independently be an aliphatic hydrocarbon group, and R ⁸² and R ⁸⁴ may each independently be an aromatic hydrocarbon group.

R ⁸¹ and R ⁸³ each independently include an aliphatic hydrocarbon group, which may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a methyl group, It may be an ethyl group, a propyl group, or a butyl group, and may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. R ⁸¹ and R ⁸³ may be different, but may be the same. The alkyl group as R ⁸¹ and R ⁸³ may have a substituent, but may not have a substituent.
R ⁸² and R ⁸⁴ are each independently an aromatic hydrocarbon group, and may be a phenyl group. The aromatic hydrocarbon group as R ⁸² and R ⁸⁴ may have a substituent, may be selected from the substituent group A described later, and may be an alkyl group having 1 to 5 carbon atoms. , An ethyl group, a propyl group or a butyl group, or a methyl group, an ethyl group, an n-propyl group or an n-butyl group.
At least one of R ⁸¹ and R ⁸³ and R ⁸² and R ⁸⁴ may be represented by the following general formula (A1-1-2).
General formula (A1-1-2)

In general formula (A1-1-2), R ^{23 to} R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamide group, or a sulfonyl group. Represents a group, a sulfonylamide group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, and R ²² and R ²⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. .
In General Formula (A1-1-2), R ^{23 to} R ²⁵ may be a hydrogen atom or a halogen atom.
In General Formula (A1-1-2), R ²² and R ²⁶ may each independently be an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, or a butyl group, or a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. Also good.
Each R ⁸⁵ may independently be a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and may be a fluorine atom or a chlorine atom. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aliphatic hydrocarbon group is exemplified by an alkyl group and an alkenyl group, and may be an alkyl group. The aromatic hydrocarbon group may be an aryl group or a phenyl group.

Specific examples of xanthene compounds are shown below, but the present invention is not limited thereto. In the following specific examples, X represents an anion. Also, any hydrogen atom in the dye structure is bonded to the polymer backbone.
Further, since the cation is delocalized in the dye structure, for example, as shown below, the cation exists on a nitrogen atom or a carbon atom of the xanthene ring.

<<<<< Cyanine Dye >>>>
The cyanine dye preferably has a partial structure derived from a compound (cyanine compound) represented by the following general formula (PM). In the present invention, the cyanine compound is a general term for compounds having a dye moiety containing a cyanine skeleton in the molecule.

In general formula (PM), ring Z1 and ring Z2 each independently represent a heterocyclic ring which may have a substituent. l represents an integer of 0 or more and 3 or less. X ⁻ represents an anion.
As a preferable range of the general formula (PM), for example, paragraphs 0077 to 0084 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein. In particular, Z1 and Z2 are each independently preferably a nitrogen-containing heterocyclic ring having a substituent, more preferably a nitrogen-containing condensed heterocyclic ring having a substituent, and more preferably an indole ring having a substituent. l is preferably 1.
In the specific examples of the cyanine dyes described in paragraphs 0077 to 0084 of JP 2013-29760 A, other sites of the dispersant (preferably described later) via any hydrogen atom in the cyanine dye structure. It is preferably bonded to R ² of the general formula (1) or L ¹ of the general formula (A), and more preferably bonded to another part of the dispersant via Z 1 or Z 2.
Specific examples of the cyanine dye are shown below, but the present invention is not limited thereto.

<<<<< Squarylium dye >>>>
As a squarylium pigment | dye, the partial structure derived from the compound (squarylium compound) represented by the following general formula (K) is preferable. In the present invention, the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.

In General Formula (K), A and B each independently represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples thereof include pyrrole, imidazole, pyrazoyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazole, indolyl and the like. Indolyl is preferred.
As a preferable range of the general formula (K), for example, paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specific examples of the squarylium dye include the following. Further, for example, paragraph 0105 of JP 2013-29760 A can be referred to. In the specific example of the squarylium dye, the other part of the dispersant (preferably R ^{2 of} the general formula (1) described later or the general formula (A) is added via any hydrogen atom in the squarylium dye structure. L ¹ ) is preferably bonded, and more preferably, it is bonded to another part of the dispersant via A or B.

In the dispersant having a dye structure used in the present invention, a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A.
(Substituent group A)
Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, linear, branched chain, or cyclic). An alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl group (preferably t-butyl group), pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1 -Norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an alkynyl group ( Preferably 2-20 carbon atoms, more preferably 2-12 carbon atoms, particularly preferably 2-8 carbon atoms. For example, propargyl, 3-pentynyl, etc.), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, for example, phenyl or naphthyl), a heterocyclic group ( Preferably it is C1-C32, More preferably, it is C1-C18 heterocyclic group, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1- Imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t- Butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy (Preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups. And, for example, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as phenoxy, 1-naphthoxy), a heterocyclic oxy group (Preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (preferably having a carbon number) 1 to 32, more preferably a silyloxy group having 1 to 18 carbon atoms. Tilsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, Dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy A group such as cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxy Ruboniruokishi),

A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group). N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexyl Sulfonyloxy), arylsulfo A ruoxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom). An acyl group having ˜24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms) And, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms) Preferably charcoal An aryloxycarbonyl group of 7 to 24, for example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as carbamoyl, N, N-diethyl Carbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably Is an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. For example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably Is preferably 6 to 32 carbon atoms Is an anilino group having 6 to 24, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridylamino) A carbonamide group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably A ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably having 36 or less carbon atoms, more preferably carbon An imide group having a number of 24 or less, for example, N-succinimide group, N-phthalimide group), alcohol Sicarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyl Oxycarbonylamino),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, more Preferably it is a C1-C24 sulfonamide group, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably carbon A sulfamoylamino group having 1 to 48, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably Has 1 to 32 carbon atoms, more preferably 1 to 2 carbon atoms. An azo group, for example, a phenylazo group, a 3-pyrazolylazo group), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexyl Thio), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, such as phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a carbon number). 1 to 18 heterocyclic thio groups, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkylsulfinyl groups (preferably having 1 to 32 carbon atoms, more preferably having 1 to 32 carbon atoms) 24 alkylsulfinyl groups such as dodecanesulfinyl), arylsulfinyl (Preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably having 1 to 24 carbon atoms) An alkylsulfonyl group, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably having 6 to 48 carbon atoms, More preferably, it is an arylsulfonyl group having 6 to 24 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 24 or less carbon atoms). Yl group, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, Phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having a carbon number) 1 to 32, more preferably a phosphinoylamino group having 1 to 24 carbon atoms, such as diethoxyphosphinoylamino, dioctyloxyphosphinoylamino), an alkyloxycarbonyloxy group (preferably having 5 to 30 carbon atoms) And more preferably an alkyloxycarbonyloxy group having 5 to 10 carbon atoms. , Thiol group and the like.
These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.
For details, for example, paragraphs 0027 to 0038 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

<<< Anion site >>>
The dye structure in the present invention includes an anion moiety.
The anion site constituting the dye structure of the dispersant having a dye structure is represented by the following general formula (A1): sulfonate anion, carboxylate anion, tetraarylborate anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ . And at least one of a group containing a structure represented by the following general formula (A2), sulfonate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) ) More preferably, it is at least one selected from a methide anion, a tetraarylborate anion, BF ⁴⁻ , PF ⁶⁻ , and SbF ⁶⁻ .
General formula (A1)
In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.
General formula (A2)
In general formula (A2), R ³ represents —SO ₂ — or —CO—; R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN.
The anion moiety may be bonded to the dye structure via a covalent bond or may be outside the molecule.

<<<< When the anion site is outside the molecule >>>>
The case where the anion moiety is outside the molecule is a case where the cation and the anion moiety are not bonded via a covalent bond but exist as separate molecules.
The anion moiety is not particularly limited, but is preferably a non-nucleophilic anion from the viewpoint of heat resistance. As the non-nucleophilic anion moiety, a known non-nucleophilic anion described in paragraph No. 0075 of JP-A-2007-310315 is preferable. Here, the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.
Examples of the anion moiety include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methide anion, a carboxylate anion, a tetraarylborate anion, —CON ⁻ CO—, —CON ^−. It is preferably at least one selected from SO ₂ −, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ and B ⁻ (CN) ₃ OCH ₃ . More preferably, it is selected from sulfonate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, BF ₄ ⁻ , PF ₆ ⁻ , and SbF ₆ ^−. Is at least one kind.
Among these, the anion site is more preferably a non-nucleophilic anion having a structure represented by the following (AN-1) to (AN-5).

In formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² may be bonded to each other to form a ring.
X ¹ and X ² each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom. 10 to 10 perfluoroalkyl groups, more preferably 1 to 4 carbon perfluoroalkyl groups, and particularly preferably a trifluoromethyl group.

In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
X ³ , X ⁴ and X ⁵ are each independently the same as X ¹ and X ² , and the preferred range is also the same.

In formula (AN-3), X ⁶ represents an alkyl group having 1 to 10 carbon atoms.
X ⁶ is preferably a C 1-10 perfluoroalkyl group, and more preferably a C 1-4 perfluoroalkyl group.

In formula (AN-4), X ⁷ represents an alkylene group having 1 to 10 carbon atoms.
X ⁷ is preferably a C 1-10 perfluoroalkylene group, and more preferably a C 1-4 perfluoroalkylene group.

In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently more preferably a halogen atom and / or a phenyl group having an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having a fluorine atom. More preferred are groups.

  100-1,000 are preferable and, as for the mass per molecule of a non-nucleophilic anion site | part, 200-500 are more preferable.

  Specific examples of the anion moiety in the second embodiment include the following, but the present invention is not limited thereto.

<<<<< when the anion moiety is bonded to the dye structure via a covalent bond >>>>
Next, a case where the anion site is bonded to the dye structure via a covalent bond will be described.
The anion site in this case is at least selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2). One is preferred.

General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
In formula (A1), at least one of R ¹ and R ² -SO ₂ - preferably represents an, both R ¹ and R ² are -SO ₂ - and more preferably represents.

The general formula (A1) is more preferably represented by the following general formula (A1-1).
Formula (A1-1)

(In general formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and X ¹ and X ² each independently represent an alkylene group or an arylene group. )
In formula (A1-1), R ¹ and R ² of the general formula (A1) in the same meaning as R ¹ and R ^2, and preferred ranges are also the same.
When X < ¹ > represents an alkylene group, 1-8 are preferable and, as for carbon number of an alkylene group, 1-6 are more preferable. When X < ¹ > represents an arylene group, 6-18 are preferable, as for carbon number of an arylene group, 6-12 are more preferable, and 6 is more preferable. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.
X ² represents an alkylene group or an arylene group, and an alkylene group is preferable. 1-8 are preferable, as for carbon number of an alkylene group, 1-6 are more preferable, 1-3 are more preferable, and 1 is especially preferable. When X ² has a substituent, it is preferably substituted with a fluorine atom. When ^one of X ¹ and X ² is the compound end, an embodiment in which the alkylene group or arylene group is an alkyl group or an aryl group is exemplified.

General formula (A2)

(In the general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN).
Preferably representing the at least two R ³ to R ⁵ is -SO ₂ - - In formula (A2), at least one of R ³ to R ⁵ -SO ₂ more preferably represents.

<<<< When Anion Site is Multimer >>>>
The anion moiety in the present invention may be a multimer. That is, the dispersant having a dye structure used in the present invention may contain a repeating unit containing an anion moiety, or the anion moiety may be a separate molecule and a multimer. As an example of the case where the anion site is a multimer, it is preferably exemplified as a repeating unit constituting the multimer in the second embodiment of the dispersant having a dye structure described later. Moreover, in 1st Embodiment mentioned later, it may be one of the repeating units which comprise P of General formula (1).
Preferable examples of the repeating unit containing an anion moiety include the repeating unit represented by the general formula (C).

General formula (C)

(In general formula (C), X ¹ represents the main chain of the repeating unit. L ¹ represents a single bond or a divalent linking group. Anion represents the anion moiety.)

In the general formula (C), X ¹ represents a main chain of repeating units, usually represents a linking group formed by polymerization reaction. Two sites represented by * are repeating units.
Specific examples of X ^1, has the same meaning as X ₁ in the repeating unit represented by the general formula (A) described below, a preferred range is also the same.

Although the specific example of the repeating unit containing an anion in this embodiment is shown below, this invention is not limited to these.

The following specific examples show a state where the anion structure is not dissociated, but it goes without saying that the state where the anion structure is dissociated is also within the scope of the present invention.

Hereinafter, preferred embodiments of the dispersant having a dye structure in the present invention will be described. Needless to say, the dispersant having a dye structure in the present invention is not limited thereto.
<< First Embodiment of Dispersant Having Dye Structure >>>>
An example of an embodiment of a dispersant having a dye structure is a structure represented by the following general formula (1).

General formula (1)
_{^{(D-R 2) n -R}} 1 - (L 1 -P) m ··· (1)
In general formula (1), R ¹ represents a (m + n) -valent linking group,
P represents a monovalent substituent having a repeating unit;
D represents the dye structure;
R ² and L ¹ each independently represents a single bond or a divalent linking group,
m represents an integer of 1 to 13,
when m is 1, P represents a monovalent substituent having two or more repeating units;
When m is 2 or more, the plurality of Ps may be different from each other, the average value of the number of repeating units constituting the plurality of Ps is 2 or more,
n represents an integer of 2 to 14,
when n is 2 or more, the plurality of D may be different from each other;
m + n represents an integer of 2 to 15.

In general formula (1), m represents an integer of 1 to 13. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
In general formula (1), n represents an integer of 2 to 14. As n, 2-8 are preferable, 2-7 are more preferable, 2-6 are especially preferable, and 2-5 are still more preferable.
In general formula (1), m + n preferably represents an integer of 2 to 15.

In general formula (1), R ¹ represents a (m + n) -valent linking group. m + n satisfies 2-15.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.

As a specific example, the (m + n) -valent linking group represented by R ¹ includes a group (which may form a ring structure) formed by combining two or more of the following structural units or the following structural units. Can be mentioned.

  The colored composition of the present invention may contain a plurality of dispersants having different m and n as the dispersant having a dye structure represented by the general formula (1). Therefore, the average value of m and n in the coloring composition of the present invention may not be an integer.

The (m + n) -valent linking group represented by R ¹ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, and 1 to 120 carbon atoms. Groups consisting of hydrogen atoms and from 0 to 10 sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.

The (m + n) -valent linking group represented by R ¹ may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide group. C1-C6 acyloxy groups such as N-sulfonylamide group and acetoxy group, C1-C6 alkoxy groups such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, methoxycarbonyl group and ethoxycarbonyl And a C2-C7 alkoxycarbonyl group such as a cyclohexyloxycarbonyl group, a carbonate group such as a cyano group and a t-butyl carbonate group, and the like.

Specific examples of the (m + n) -valent linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  The (m + n) -valent linking group is preferably (1), (2), (10), (11), (16) to (20), or (26) to (29).

In general formula (1), R ² and L ¹ each independently represents a single bond or a divalent linking group. When a plurality of R ² and L ¹ are present, they may be the same or different.
Divalent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the divalent linking group include a group constituted by combining two or more of the following structural units or the following structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and A divalent linking group consisting of 0 to 10 sulfur atoms is preferred. More preferably, a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 It is a divalent linking group consisting of from 1 to 7 sulfur atoms. More preferably, a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 It is a divalent linking group consisting of from 1 to 5 sulfur atoms.

The divalent linking group represented by R ² may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide group. C1-C6 acyloxy groups such as N-sulfonylamide group and acetoxy group, C1-C6 alkoxy groups such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, methoxycarbonyl group, ethoxy Examples thereof include C2-C7 alkoxycarbonyl groups such as carbonyl group and cyclohexyloxycarbonyl group, and carbonate ester groups such as cyano group and t-butyl carbonate group.

In general formula (1), P represents a monovalent substituent having two or more repeating units. When m is 2 or more, m Ps may be the same or different.
When m is 1, P represents a monovalent substituent having 2 or more repeating units (preferably 2 to 100, more preferably 2 to 50, still more preferably 2 to 20). When m is 2 or more, the average number of m repeating units of P is 2 or more (preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 20). It is. According to this aspect, the flatness of the coating film is improved.
The number of repeating units when m is 1, and when m is 2 or more, the average value of the number of m repeating units can be determined by NMR (Nuclear Magnetic Resonance). Specifically, for example, m can be calculated from the peak area ratio between the (m + n) -valent linking group represented by R ¹ and the dye structure D, and the peak area ratio of the repeating unit can be calculated by dividing by m. .

  Examples of the repeating unit constituting P include a repeating unit containing an alkali-soluble group such as an acid group, a repeating unit containing a polymerizable group, a repeating unit derived from a macromonomer, etc., and an alkali-soluble group such as an acid group. It is preferable to include at least a repeating unit. Each of these repeating units may contain only one type or two or more types. Hereinafter, these repeating units will be described in detail.

<<<<< Repeating unit containing an acid group >>>>
Examples of the acid group of the repeating unit containing an acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. One type of acid group contained in the repeating unit containing an acid group may be contained, or two or more types may be contained.
When P contains a repeating unit containing an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is preferably 10 to 80 mol with respect to 100 mol of the repeating unit constituting P, and 10 to 65 Mole is more preferred.

<<<<< Repeating unit containing other alkali-soluble groups >>>>
Examples of the repeating unit containing another alkali-soluble group include a repeating unit containing a phenolic hydroxyl group and the like.
Further, P preferably contains a repeating unit having a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains in the side chain (hereinafter sometimes referred to as “(b) repeating unit”). .
(B) The number of repeating alkyleneoxy chains in the repeating unit is preferably 2 to 10, more preferably 2 to 15, and still more preferably 2 to 10.
One alkyleneoxy chain is represented by — (CH ₂ ) _n O—, and n is an integer, but n is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 or 3.
In the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, only one kind of alkyleneoxy chain may be contained, or two or more kinds may be contained.
(B) The repeating unit is preferably represented by the following general formula.

(Wherein X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and P represents a group containing a group consisting of repeating alkyleneoxy chains.)
X ¹ and L ¹ in the general formula (P) have the same meanings as X1 and L1 in the general formula (A), respectively, and preferred ranges thereof are also the same.
P represents a group containing a group consisting of repeating alkyleneoxy chains, more preferably a group consisting of repeating alkyleneoxy chains-terminal atom or terminal group.
The terminal atom or terminal group is preferably a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a hydroxyl group, a hydrogen atom, a methyl group, a phenyl group and A hydroxyl group is more preferred, and a hydrogen atom is particularly preferred.

Examples of the repeating unit (b) are shown below, but are not limited thereto.

When P includes a repeating unit containing another alkali-soluble group, for example, 10 to 80 mol is preferable and 10 to 65 mol is more preferable with respect to 100 mol of the repeating unit constituting P.
Moreover, the ratio of the repeating unit containing all alkali-soluble groups including an acid group or another alkali-soluble group is preferably, for example, 10 to 80 mol, and 10 to 65 mol with respect to 100 mol of the repeating unit constituting P. More preferred.

<<<<< Repeating unit containing a polymerizable group >>>>
As the polymerizable group contained in the repeating unit containing a polymerizable group, a known polymerizable group that can be crosslinked by a radical, an acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (Epoxy group, oxetane group), methylol group and the like are mentioned, but a group containing an ethylenically unsaturated bond is particularly preferable, (meth) acryloyl group is more preferable, glycidyl (meth) acrylate and 3,4-epoxycyclohexyl. A (meth) acryloyl group derived from methyl (meth) acrylate is more preferred.

  As a method for introducing a polymerizable group, (1) (a) a method in which a polymerizable group such as a repeating unit is introduced by modifying a repeating unit to be introduced with a polymerizable group-containing compound, and (2) a polymerizable group-containing compound is commonly used. There are methods such as polymerization and introduction.

When included, the amount of the polymerizable group contained in the dispersant having a dye structure is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, relative to 1 g of the dye structure. 0.3 to 1.0 mmol is particularly preferable.
Moreover, when P contains the repeating unit containing a polymeric group, 5-40 mol is preferable with respect to 100 mol of all the repeating units which comprise P, and 5-35 mol is more preferable.

  Specific examples of the repeating unit having a polymerizable group include the following. However, the present invention is not limited to these.

<<<<< Repeating unit derived from macromonomer >>>>
The repeating unit derived from the macromonomer is preferably a repeating unit derived from the ethylenically unsaturated monomer. One type of repeating unit derived from the macromonomer may be included, or two or more types may be included.
The weight average molecular weight of the repeating unit derived from the macromonomer is preferably 1,000 or more and 50,000 or less, more preferably 1,000 or more and 20,000 or less, still more preferably 2,000 or more and 10,000 or less, 000 or more and 5,000 or less are particularly preferable.

As a repeating unit derived from a macromonomer, a repeating unit having a polyester-based macromonomer moiety that is excellent in flexibility and solvophilicity is a pigment dispersibility, dispersion stability, and development exhibited by a coloring composition using a pigment dispersion. From the viewpoint of sex.
The repeating unit derived from the macromonomer is preferably represented by the following general formula (b-3A), more preferably represented by the following general formula (b-3B), and the following general formula (b-3C). It is further preferred that
General formula (b-3A)

(In the general formula (b-3A), R ^3A represents a hydrogen atom or a methyl group. L ^3A represents a single bond or a divalent linking group. A ^3A has (b-3) a weight average molecular weight of 1,000 to 50,000. The following parts are represented.)
In the general formula (b-3A), when L ^3A represents a divalent linking group, the divalent linking group is at least one selected from an alkylene group, an arylene group, and a heteroarylene group, or these group and -NH -, - CO -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - a combination of at least one group selected from - S- and -SO ₂ comprising group, and particularly, an alkylene group, -CO ₂ - and, a -CO-, preferably a group comprising a combination of -CONH-.

General formula (b-3B)

(In general formula (b-3B), R ^3A represents a hydrogen atom or a methyl group, L ^3A represents a single bond or a divalent linking group, R ^3B represents an alkylene group, and R ^3C represents an alkyl group. N represents an integer of 5 to 100.)
In General Formula (b-3B), L ^3A has the same meaning as L ^{3A in} General Formula (b-3A) described above, and the preferred range is also the same.
In the general formula (b-3B), R ^3B is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably a linear alkylene group having 1 to 10 carbon atoms, and an unsubstituted 5-carbon group. 20 straight-chain alkylene groups are more preferred, and — (CH ₂ ) ₅ — is particularly preferred.
In general formula (b-3B), R ^3C is preferably a linear or branched alkyl group having 5 to 20 carbon atoms.
In general formula (b-3B), n represents the integer of 5-100, and the integer of 5-80 is preferable.

General formula (b-3C)

(In the general formula (b-3C), R ^3A represents a hydrogen atom or a methyl group. R ^3B represents an alkylene group. R ^3C represents an alkyl group. N represents an integer of 5 to 100.)
In the general formula ^{(b-3C), R 3A} , R 3B, R 3C and n, R ^3A in general formula ^{(b-3B), R 3B} , have the same meaning as R ^3C and n, the preferable ranges It is the same.
The following formula is mentioned as an example of the repeating unit derived from a macromonomer. In the following formula, n is an integer of 5 to 100. For example, n = 10, n = 30, n = 50 and the like are preferable examples.

Commercially available macromonomers, for example, repeating units derived from AA-6 manufactured by Toa Gosei are also examples of preferred repeating units derived from the macromonomer in the present invention.
When P contains a repeating unit derived from a macromonomer, the ratio is preferably 3 to 20 mol with respect to 100 mol of all repeating units.

<<<<< other repeating unit >>>>
P in the present invention may have a repeating unit other than the repeating units described above. Specifically, the repeating unit that may be contained in P includes a lactone group, an acid anhydride group, an amide group, —COCH ₂ CO—, a development promoting group such as a cyano group, a long chain and a cyclic alkyl group, Examples thereof include a repeating unit containing at least one selected from an aralkyl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, an affinity control group such as an amino group, and the like.
These may be included in only one type, or may be included in two or more types.
Examples of the introduction method include a method in which the dye structure is introduced in advance and a method in which a monomer having the above group is copolymerized.
When P contains another repeating unit, the ratio is preferably 3 to 20 mol with respect to 100 mol of all repeating units.

  Although the specific example of the repeating unit containing the acid group mentioned above or other repeating units is shown, this invention is not limited to this. Needless to say, repeating units derived from M-10, O-6, O-7, etc. used in the examples described later are also used as preferred examples.

  In general formula (I), D represents the dye structure described above. The preferred range is also synonymous.

<< Synthesis Method of Dispersant Having Dye Structure Represented by General Formula (1) >>
The dispersant having the dye structure represented by the general formula (1) can be synthesized by the following method.
(1) A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group or the like is introduced at the end, an acid halide having a dye structure, an alkyl halide having a dye structure, an isocyanate having a dye structure, or the like. Polymer reaction method.
(2) A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a dye structure are subjected to a Michael addition reaction.
(3) A method of reacting a polymer having a carbon-carbon double bond introduced at the terminal thereof with a mercaptan having a dye structure in the presence of a radical generator.
(4) A method of reacting a polymer having a plurality of mercaptans introduced at its terminal with a compound having a carbon-carbon double bond and a dye structure in the presence of a radical generator.
(5) A method in which a vinyl compound is radically polymerized in the presence of a thiol compound having a dye structure.
Among the above, the synthesis methods (2) to (5) are preferable and the synthesis methods (3) to (5) are more preferable because of ease of synthesis.

  More specifically, the synthesis method (5) is preferably a radical polymerization method in the presence of a compound represented by the following general formula (3).

^{(D-R 4 - (S} ) p) n -R 3 - (SH) m ··· (3)
In general formula (3), R ³ represents an (m + n) -valent linking group, D represents a dye structure, R ⁴ represents a single bond or a divalent linking group, and S represents a sulfur atom. And SH represents a thiol group, m represents an integer of 1 to 13, n represents an integer of 2 to 14, and when n is 2 or more, a plurality of D may be different from each other, m + n represents an integer of 2 to 15, and p represents 0 or 1.

In general formula (3), D is synonymous with D in general formula (1), and its preferable aspect is also the same.
In the general formula (3), R ³ has the same meaning as R ¹ in the general formula (1), a preferable embodiment thereof is also the same.
In general formula (3), R ⁴ has the same meaning as R ² in general formula (1), and the preferred embodiment is also the same.
In general formula (3), m and n have the same meanings as m and n in general formula (1), respectively, and the preferred embodiments are also the same.
In general formula (3), p represents 0 or 1.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method (7) is more preferable from the viewpoint of ease of synthesis.
(6) A method of converting a halide compound having a dye structure into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a method of reacting with CH ₃ COSNa and hydrolyzing, etc.) )
(7) A method in which a compound having a dye structure and a functional group capable of reacting with a mercapto group is added to a compound having 2 to 15 mercapto groups in one molecule.

Suitable examples of the “functional group capable of reacting with a mercapto group” in (7) above include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the compound having 2 to 15 mercapto groups in one molecule include the following compounds.

  Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, particularly preferred compounds are (S-1), (S-2), (S-10), (S- 11), (S-16) to (S-20), and (S-26) to (S-29).

  The radical addition reaction product of “a compound having 2 to 15 mercapto groups in one molecule” and “a compound having a dye structure and a functional group capable of reacting with a mercapto group” is, for example, Are dissolved in a suitable solvent, and the radicals are dissolved in a radical solvent. The “compound having 2 to 15 mercapto groups in one molecule” and “the compound having a dye structure and having a functional group capable of reacting with a mercapto group” It is obtained using a method (thiol-ene reaction method) in which a generator is added and added at about 50 to 100 ° C.

Examples of suitable solvents used in the thiol-ene reaction method include “a compound having 3 to 10 mercapto groups in one molecule”, “a functional group having a dye structure and capable of reacting with a mercapto group”. It can be arbitrarily selected according to the solubility of the “compound having” and the “radical addition reaction product to be produced”.
For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate Azo compounds such as benzoyl peroxide, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

Although it does not restrict | limit especially as a vinyl compound used with the synthesis method of said (5), For example, the thing similar to the vinyl compound used when obtaining the substituent represented by P of the said General formula (1) is used. It is done.
Only one vinyl compound may be polymerized, or two or more vinyl compounds may be used in combination.
Moreover, when applying to the photocurable composition which needs an alkali image development process, the vinyl compound which has 1 or more types of acid groups, and the vinyl compound which does not have 1 or more types of acid groups may be copolymerized. More preferred.

In particular, it is preferable to perform polymerization according to a conventional method using a vinyl compound and a compound represented by the general formula (3) by a known method. In addition, the compound represented by the general formula (3) functions as a chain transfer agent, and may be simply referred to as “chain transfer agent” hereinafter.
For example, a method in which these vinyl compound and chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include 2,2′-azobis (isobutyronitrile), 2,2′-azobis- (2,4′-dimethylvaleronitrile), and dimethyl 2,2′-azobisisobutyrate. Other azo compounds, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.

<<< Second Embodiment of Dispersant Having Dye Structure >>>
Another embodiment of the dispersant having a dye structure is exemplified by a multimer containing a repeating unit having a dye structure (hereinafter sometimes referred to as “(a) repeating unit”).

(A) The skeleton structure of the repeating unit is not particularly defined, but is represented by general formula (A), general formula (B), and general formula shown in paragraph numbers 0276 to 0304 of JP2013-28764A. It is preferable that at least one of the repeating units represented by (C) is a skeleton, or a multimer represented by the general formula (D) is preferable. The description of paragraph numbers 0276 to 0304 of JP2013-28764 is incorporated in the present specification.
The dispersant having a dye structure preferably includes a multimer containing a repeating unit represented by the following general formula (A) in the skeleton structure of the repeating unit (a).
The ratio of the repeating unit having a dye structure is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, based on all repeating units constituting the multimer.

Repeating unit represented by formula (A)

(In general formula (A), X ₁ represents a linking group formed by polymerization, L ₁ represents a single bond or a divalent linking group, and Dye I represents a dye structure.)

In general formula (A), X ₁ represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units. X ₁ is preferably —CH ₂ —CH ₂ — or —CH ₂ —C (CH ₃ ) —. When L ₁ represents a divalent linking group, the divalent linking group may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group). Etc.), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthylene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—. , —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof. Represents a linking group containing —COO— or a phenylene group.
The structure of the X ₁ -L ₁ moiety is particularly preferably a linking group represented by the following (XX-1) to (XX-24), and represented by (XX-1) and (XX-2) (meta ) Acrylic linking chain, styrene linking chains represented by (XX-10) to (XX-17), (XX-18) and (XX-19), and vinyl represented by (XX-24) It is more preferable to be selected from a system linking chain, and it is represented by (XX)-(XX-10) to (XX-17) (meth) acrylic linking chains represented by (XX-1) and (XX-2). More preferably, the styrenic linking chain is selected from vinyl linking chains represented by (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2) and A styrene-based connecting chain represented by (XX-11) is more preferable.
In (XX-1) to (XX-24), it represents that L ₁ is linked at the site indicated by *.
Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In general formula (A), DyeI represents the dye structure described above.

The multimer containing the repeating unit represented by the general formula (A) is (1) a method of synthesizing a monomer having a dye structure by addition polymerization, and (2) a high reaction such as an isocyanate group, an acid anhydride group or an epoxy group. It can be synthesized by a method of reacting a polymer having a reactive functional group with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with a highly reactive group.
Known addition polymerizations (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, but among these, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye structure is not decomposed. Known reaction conditions can be applied to the radical polymerization. That is, the multimer used in the present invention is preferably an addition polymer.
Among them, the multimer having the repeating unit represented by the general formula (A) in the present invention is a radical obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. A polymer is preferred.

Examples of the repeating unit (a) preferably used in the present invention are shown below. Needless to say, the present invention is not limited to these examples. X ⁻ represents an anion site. Further, although some X ⁻ are shown in a state where the anion structure is not dissociated, it is needless to say that the dissociated state is also included in the present invention.

The dispersant having a dye structure in the second embodiment may have other repeating units in addition to the repeating unit (a) such as the repeating unit represented by the general formula (A). It is preferable to have a repeating unit.
Examples of the other repeating unit include a repeating unit containing an alkali-soluble group such as an acid group, a repeating unit containing a polymerizable group, a repeating unit derived from a macromonomer, and the like, and a repeating unit containing an alkali-soluble group such as an acid group It is preferable to contain at least. With respect to these repeating units, the respective repeating units described in the first embodiment of the dispersant having the above-described dye structure can be adopted, and preferred ranges thereof are also the same. In addition, other repeating units other than the above-described repeating units may be included, and each of the repeating units described in the first embodiment of the dispersant having the dye structure described above may be included in the other repeating units. The preferred range is also the same.
In the case where the dispersant having a dye structure in the second embodiment includes a repeating unit containing an acid group, the ratio is preferably 10 to 80 mol%, more preferably 10 to 65 mol% of all repeating units.
When the dispersing agent having a dye structure in the second embodiment includes a repeating unit containing another alkali-soluble group, the ratio is preferably 10 to 80 mol%, and 10 to 65 mol% of all repeating units. More preferred.
The dispersant having the dye structure in the second embodiment contains an acid group or other alkali-soluble group, and the ratio of the repeating units containing all alkali-soluble groups is preferably 10 to 80 mol% of all repeating units, 10-65 mol% is more preferable.
When the dispersing agent having a dye structure in the second embodiment includes a repeating unit having a polymerizable group, the ratio is preferably 5 to 40 mol%, more preferably 5 to 35 mol%, based on all repeating units.
When the dispersant having a dye structure in the second embodiment includes a repeating unit derived from a macromonomer, the ratio is preferably 3 to 20 mol% of all repeating units.
In the case where the dispersant having a dye structure in the second embodiment includes other repeating units, the ratio is preferably 3 to 20 mol with respect to 100 mol of all repeating units.

<<<< Various Properties of Dispersant Having Dye Structure >>>>
The weight average molecular weight of the dispersant having a dye structure is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. The upper limit is preferably 50000 or less, more preferably 40000 or less, and further preferably 30000 or less. By satisfy | filling the said range, color transfer property becomes more favorable. Furthermore, developability is improved and development residues can be further reduced.

  The acid value of the dispersant having a dye structure is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 27 mgKOH / g or more, and particularly preferably 30 mgKOH / g or more. The upper limit of the acid value is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, further preferably 180 mgKOH / g or less, still more preferably 130 mgKOH / g or less, and still more preferably 120 mgKOH / g or less. By satisfy | filling the said range, developability improves more and a development residue can be reduced more.

The method for measuring the specific absorbance of the dispersant having a dye structure is, for example, that the maximum absorbance at 400 nm to 800 nm is 1.0 using a solvent having sufficient solubility in the dispersant having the dye structure. And a method of adjusting the concentration of a solution containing a dispersant having a dye structure and measuring the absorbance of the solution at 25 ° C. using a cell having an optical path length of 1 cm. As the solvent for measuring the specific absorbance, a solvent having sufficient solubility for the dispersant having a dye structure can be appropriately used. Preferred solvents include tetrahydrofuran, methanol, isopropyl alcohol, dimethyl sulfoxide, acetonitrile, ethyl acetate, hexane, toluene, water, concentrated sulfuric acid, methanesulfonic acid and the like. Tetrahydrofuran is used when tetrahydrofuran has sufficient solubility.
The specific absorbance represented by the above formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm is 5 or more, preferably 10 or more, more preferably 20 or more, and particularly preferably 25 or more. The upper limit is not particularly defined, but is usually 99 or less.

  The dispersant having a dye structure may be used alone or in combination of two or more.

<< Pigment >>
As the pigment, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferably used. The pigment preferably has a high transmittance.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like, or carbon black (CI Pigment Black 7). Specific examples of the metal compound include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal composite oxides.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,179,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1; and the like.

Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment Black 1

  These organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment A mixture of these can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50, and more preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the desired spectrum.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, and more preferably 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment alone or a mixture of this with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100.

  Further, as the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

When used for a color filter, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle diameter of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle diameter of the pigment refers to a value measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)).
Among these, the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments.
In particular, C.I. I. Pigment red 177 (anthraquinone pigment), C.I. I. Pigment red 254 (diketopyrrolopyrrole pigment), C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment Blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment Blue 15: 3 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139,185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment Violet 23 (dioxazine pigment) is preferred, and C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 6 is more preferable.

The content of the pigment is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 1 to 15% by mass in the pigment dispersion. Moreover, 40 mass parts or more are preferable with respect to 100 mass parts of dispersing agents which have a pigment structure, 50 mass parts or more are more preferable, 80 mass parts or more are more preferable, 100 mass parts or more are especially preferable. The upper limit is preferably 600 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, and more preferably 150 parts by mass with respect to 100 parts by mass of the dispersant having a dye structure. Part or less is particularly preferable. 80-150 mass parts is especially preferable.
The pigment dispersion of the present invention may contain only one type of pigment or two or more types of pigment. When two or more types are included, the total amount is preferably within the above range.

<< Solvent >>
The solvent contained in the pigment dispersion is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but the solubility, coating property, and safety of the dispersant having a dye structure are not limited. It is preferable to select in consideration of the properties. The solvent is preferably an organic solvent.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), -Oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2 -Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate Etc., and ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons, For example , Toluene, xylene and the like are preferable.

  Two or more of these organic solvents may be mixed from the viewpoints of solubility of a dispersant having a dye structure and the like, and improvement of the coated surface.

The content of the solvent in the pigment dispersion is preferably such that the total solid concentration of the pigment dispersion is 5% to 80% by mass, and 5% to 50% by mass from the viewpoint of applicability. More preferable is an amount of 10 to 30% by mass.
The pigment dispersion may contain only one type of solvent or two or more types of solvents. When two or more types are included, the total amount is preferably within the above range.

<Method for producing pigment dispersion>
The method for producing a pigment dispersion of the present invention includes a step of dispersing a pigment in the presence of a dispersant having a dye structure, and the dispersant having a dye structure is a triarylmethane dye, a xanthene dye, a cyanine dye, and a squarylium dye. The dispersant having the dye structure selected from the above is a dye multimer having two or more dye structures in the same molecule, and is represented by the following formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm. The specific absorbance expressed is 5 or more.
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of a dispersant having a dye structure in a solution, the unit of which is expressed in mg / ml.
The dispersant and pigment having a dye structure are synonymous with the above-described dispersant and pigment having a dye structure, and the preferred range is also the same.
As a dispersion method, for example, it is preferable to mix a dispersion containing a dispersant having a dye structure, a pigment, and a solvent with a bead mill, and to perform dispersion treatment using a disperser.

<Composition>
The composition of the present invention is a composition containing a pigment and a solvent with respect to 100 parts by mass of the resin represented by the general formula (1),
The resin has a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes;
The resin is a composition having a specific absorbance of 5 or more represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm.
The composition of the present invention is a composition containing 80 to 150 parts by mass of a pigment and a solvent with respect to 100 parts by mass of the resin including the repeating unit represented by the general formula (A), and the resin Has a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes,
The resin is a composition having a specific absorbance of 5 or more represented by the following formula (Aλ) at a maximum absorption wavelength at 400 nm to 800 nm.
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c is a composition representing the concentration of a resin having a dye structure in a solution, the unit of which is expressed in mg / ml.
Such a composition is used as the pigment dispersion of the present invention. The preferred range of the composition is the same as the preferred range of the corresponding pigment dispersion.

<Coloring composition>
The colored composition of the present invention contains the pigment dispersion and a curable compound (polymerizable compound, thermosetting compound, polyfunctional thiol compound, alkali-soluble resin, etc.). The total content of the curable compound in the coloring composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and 5 to 20% by mass with respect to the total solid content of the coloring composition. You can also.
The coloring composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
By setting it as such a structure, it is preferably used as a coloring composition for color filters.
Moreover, it is preferable that the coloring composition of this invention contains a photoinitiator. Furthermore, other dispersants other than the dispersant having the dye structure, a polymerization inhibitor, a surfactant, and the like may be included.
The content of the pigment dispersion in the colored composition of the present invention is set in consideration of the content ratio with the pigment described later.
The amount of the pigment dispersion in the coloring composition is preferably such that the solid content of the pigment dispersion is 10 to 80% by mass, and 30 to 70% by mass with respect to the total solid content of the coloring composition. Is more preferable, and the amount of 40 to 60% by mass is even more preferable.
The coloring composition of the present invention may contain only one type of pigment dispersion, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
25 mass% or more is preferable with respect to the total solid of a coloring composition, and, as for content of the pigment in a coloring composition, 30 mass% or more is more preferable. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.
60 mass% or more is preferable with respect to the total solid of a coloring composition, and, as for the sum total of content of the dispersing agent which has a pigment | dye structure in a coloring composition, and a pigment, 65 mass% or more is more preferable. The upper limit is preferably 99% by mass or less, and usually 90% by mass or less.

<<< polymerizable compound >>>
As the polymerizable compound, a known polymerizable compound that can be crosslinked by a radical, an acid, or heat can be used. For example, polymerizable compounds containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol and the like can be mentioned. The polymerizable compound is suitably selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, from the viewpoint of sensitivity. Among them, a polyfunctional polymerizable compound having 4 or more functional groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.

  Such a group of compounds is widely known, and these can be used without any particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. In addition, 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. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

  As the polymerizable compound, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is also preferable. As an example, paragraph 0227 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.

  Further, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, compounds described in paragraph numbers 0254 to 0257 of JP-A-2008-292970 Which is incorporated herein by reference.

  Among them, as a polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku), Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku), ethyleneoxy modified di Pentaerythritol hexaacrylate (A-DPH-12E as a commercial product; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, from Sartomer Are, SR454, SR494, SR499) it is preferred. These oligomer types can also be used. SR368 (manufactured by Sartomer) and KAYARAD D-330 (manufactured by Nippon Kayaku) are also preferred. Preferred embodiments of the polymerizable compound are shown below.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the polymerizable compound has an unreacted carboxyl group or the like, it can be used as it is. However, if necessary, a non-aromatic carboxylic acid anhydride is reacted with the hydroxyl group of the polymerizable compound. An acid group may be introduced. Specific examples of non-aromatic carboxylic acid anhydrides include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. .

  As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei.

Although the polymeric compound which has an acid group may be used individually by 1 type, since it is difficult to use a single compound on manufacture, you may mix and use 2 or more types.
A preferable acid value of the polymerizable compound having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g. When the acid value of the polyfunctional monomer is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability such as the surface smoothness of the pixels is excellent. Therefore, when two or more kinds of polymerizable compounds having different acid groups are used in combination, or when a polymerizable compound having no acid group and a polymerizable compound having an acid group are used in combination, the acid value as the entire polymerizable compound is It is preferable to adjust so that it may enter into the said range.

Moreover, it is also a preferable aspect to contain the polymeric compound which has a caprolactone structure as a polymeric compound.
The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

  In general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In General Formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and “*” represents a bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Polymerizable compounds having a caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), the formula (Z- 2) The number of groups represented by 2 = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (same formula, m = 1, the number of groups represented by formula (Z-2) = 3, Compound in which R ¹ is all hydrogen atoms), DPCA-60 (formula, m = 1, number of groups represented by formula (Z-2) = 6, compound in which R ¹ is all hydrogen atoms), DPCA -120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polymeric compound which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  Moreover, the compound represented by the following general formula (Z-4) or (Z-5) can also be used for the polymerizable compound.

In the formula (Z-4) and (Z-5), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) yCH (} CH 3) O) - a And y independently represents an integer of 0 to 10, and X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (Z-4), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. . However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (Z-5), the sum total of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. . However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side A form in which the terminal of X is bonded to X is preferred.

  The compound represented by general formula (Z-4) or general formula (Z-5) may be used individually by 1 type, and may be used together 2 or more types. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), among which exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by general formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains made by Sartomer, manufactured by Nippon Kayaku. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

  In the present invention, a compound having an epoxy group can also be used as the polymerizable compound. As the compound having an epoxy group, one having two or more epoxy groups in one molecule is preferable. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be achieved more effectively. The number of epoxy groups is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3 in one molecule.

As the epoxy compound, the description in paragraphs 0091 to 0103 of JP-A No. 2014-153554 can be referred to, and the contents thereof are incorporated in the present specification.
As a commercial product of an epoxy compound, for example, as a bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON860 , EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation), etc., and as bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602 (Nippon Kayaku Co., Ltd.), etc., and phenol novolac type epoxy resins include JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N- 770, EPICLON N-775 (manufactured by DIC Corporation) and the like, and cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N- 680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and ADEKA RESIN EP- 080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Chemical Industries, Ltd.) ), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
Moreover, as a commercial item of the compound which has an epoxy group, JER1031S (made by Mitsubishi Chemical Corporation), JER1032H60 (made by Mitsubishi Chemical Corporation), EPICLON HP-4700 (made by DIC Corporation), EPICLON N-695. (Made by DIC Corporation) etc. can also be used preferably.

In the present invention, the polymerizable compound is described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. is there. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds. By using the compounds, it is possible to obtain a colored composition having an extremely excellent photosensitive speed.
In the present invention, a compound having an oxetane group can also be used as the polymerizable compound. Examples of the compound having an oxetane group include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein. As specific examples, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA -306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei) and the like.

When the polymerizable composition contains a polymerizable compound, the content of the polymerizable compound is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, based on the total solid content of the colored composition. -20 mass% is further more preferable.
The coloring composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polyfunctional thiol compound >>
The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (TI).
General formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a 2 to 4 valent linking group.)

  In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

  When the coloring composition of this invention contains a polyfunctional thiol compound, 0.3-8.9 mass% is preferable with respect to the total solid except a solvent, and 0.8-6.4 mass% is more preferable. .

<< photopolymerization initiator >>
The colored composition of the present invention may further contain a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketones. At least one compound selected from the group consisting of a compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is particularly preferable, and an oxime compound is more preferable.

In particular, when the colored composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, a stepper exposure machine is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator used in the present invention, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated herein.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE OXE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used. Further, as the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are suitably used as photopolymerization initiators in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
In a commercial item, IRGACURE-OXE-01 (product made from BASF) and IRGACURE-OXE-02 (product made from BASF) which show the structure below are used suitably, for example. Also, TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In general formula (OX-1), as a bivalent organic group represented by A, a C1-C12 alkylene group, a cycloalkylene group, and an alkynylene group are preferable. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

  Specific examples (C-4) to (C-13) of the compound represented by the general formula (OX-1) are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Varian Carry-5 spectrophotometer), an ethyl acetate solvent is used, and 0.01 g / It is preferable to measure at the concentration of L.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

When the coloring composition of this invention contains a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid of a coloring composition, More preferably, it is 0.5. It is -30 mass%, More preferably, it is 1-20 mass%.
The colored 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.

<< Other dispersant other than the dispersant having a dye structure >>
The coloring composition of the present invention may further contain a dispersant other than the dispersant having a dye structure.
Other dispersants include polymer dispersants [eg, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) Acrylic copolymer, naphthalene sulfonic acid formalin condensate], surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, and pigment derivatives. Details of these can be referred to the descriptions in paragraphs 0045 to 0049 of JP-A-2014-130173, and the contents thereof are incorporated in the present specification.

In a coloring composition, when it contains another dispersing agent, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments as a total content of another dispersing agent, and 5-70 mass parts is. More preferred is 10 to 60 parts by mass.
In the present invention, in particular, it may be configured so as not to contain other dispersants. The composition which does not substantially contain means that an amount of a level capable of functioning as a pigment dispersant is not blended, for example, 1% by mass or less of the total dispersant.
Another dispersing agent may be used independently and may be used in combination of 2 or more type. When two or more types are included, the total amount is preferably within the above range.

<< Alkali-soluble resin >>
The coloring composition of the present invention may further contain an alkali-soluble resin.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility 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 a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.

  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. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

  Examples of monomers that can impart an acid group after polymerization include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth). And monomers having an isocyanate group such as acrylate. Only one type of monomer for introducing these acid groups may be used, or two or more types may be used. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization may be polymerized as a monomer component.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  As the alkali-soluble resin, a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”) are essential. It is also preferable to include a polymer (a) obtained by polymerizing the monomer component.

In General Formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
General formula (ED2)

In General Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP 2010-168539 A can be referred to.

Thereby, the coloring composition of this invention can form the cured coating film which was very excellent also in transparency with heat resistance. In the general formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, but for example, methyl, ethyl, n Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoe Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butylsilane) Rohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

The alkali-soluble resin may contain a repeating unit derived from an ethylenically unsaturated compound represented by the following formula (X) and / or a repeating unit derived from a compound represented by the general formula (ED).
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 from 1 to 20, preferably from 1 to 10, the 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.

In General Formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
General formula (ED2)
In General Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP 2010-168539 A can be referred to.

  Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the alkali-soluble resin containing a polymerizable group as described above include a dial NR series (manufactured by Mitsubishi Rayon), a Photomer 6173 (manufactured by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Biscote R-264, Examples thereof include KS resist 106 (all manufactured by Osaka Organic Chemical Industry), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries), and Ebecryl 3800 (manufactured by Daicel UCB). As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting compound having polymerizable group, JP 2002-229207 A Resin obtained by basic treatment of a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable. Further, ACRYCURE-RD-F8 (manufactured by Nippon Shokubai) is also preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers is suitable. . In addition, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2 described in JP-A-7-140654 -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Gerare, particularly preferred examples include a copolymer of benzyl methacrylate / methacrylic acid.

As the alkali-soluble resin, paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to <0685> to <0700> of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Are incorporated herein.
Furthermore, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, No. 024934, paragraph numbers 0132 to 0143 described in paragraphs 0132 to 0143 and the binder resins used in the examples, JP 2011-242752A paragraphs 0092 to 0098 and the binder resins used in the examples, Paragraph No. of Kokai 2012-032770 It preferred to use a binder resin according to 030-0072. These contents are incorporated herein. More specifically, the following resins are preferable.

The lower limit of the acid value of the alkali-soluble resin is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, more preferably 45 mgKOH / g or more, more preferably 55 mgKOH / g or more, and more preferably 80 mgKOH / g or more. Preferably, 130 mgKOH / g or more is more preferable. As an upper limit, 250 mgKOH / g or less is preferable and 210 mgKOH / g or less is more preferable.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin is preferably 1 to 15% by mass, more preferably 2 to 12% by mass with respect to the total solid content of the coloring composition. And particularly preferably 3 to 10% by mass.
The coloring composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< Solvent >>>
As the solvent, the solvents mentioned above for the pigment dispersion can be used.
The content of the solvent in the colored composition is preferably such that the total solid concentration of the colored composition is 5 to 80% by mass, more preferably 5 to 50% by mass, and 10 to 30% by mass. % Is more preferred.
The coloring composition may contain only one type of solvent or two or more types of solvents. When two or more types are included, the total amount is preferably within the above range.

<<< Polymerization inhibitor >>>
In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the coloring composition of this invention contains a polymerization inhibitor, about 0.01-5 mass% is preferable with respect to the mass of a coloring composition.
The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< surfactant >>>
Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the coloring composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. Liquidity can be further improved.
That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC), Florard FC430, FC431, FC171 (above, Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) Etc.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5 manufactured by BASF) 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), SO Sparse 20000 (Lubrizol), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. . 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical), W001 (manufactured by Yusho) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, and “Toray Silicone SH29PA” manufactured by Toray Dow Corning. , “Tole Silicone SH30PA”, “Tole Silicone SH8400”, Momentive Performance Materials “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-4442”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone, “BYK307”, “BYK323”, “BYK330” manufactured by BYK Chemie, and the like.
When the coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.001%, based on the total mass of the coloring composition. 005 to 1.0% by mass.
The coloring 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.

<< other ingredients >>
The colored composition of the present invention further contains other components such as a dye, a crosslinking agent, an organic carboxylic acid, and an organic carboxylic acid anhydride as long as the effects of the present invention are not impaired in addition to the above-described components. May be.

<< Dye >>
The coloring composition of the present invention may contain a known dye. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Toho 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No., U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. The chemical structure includes pyrazole azo, pyromethene, anilinoazo, triarylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc. Dyes can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

<<< crosslinking agent >>>
You may make the coloring composition of this invention contain a crosslinking agent. By containing a crosslinking agent, the hardness of the cured film obtained can be further increased.
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, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. 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 coloring composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, and 3 to 20% by mass of the total solid content of the composition. More preferred.
The coloring composition of the present invention may contain only one type of cross-linking agent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<<< Organic carboxylic acid, organic carboxylic acid anhydride >>>
The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride. As specific examples of the organic carboxylic acid and the organic carboxylic acid anhydride, for example, paragraphs 0338 to 0340 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated herein.
When the colored composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the amount of the organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by weight in the total solid content. , Preferably 0.03 to 5% by weight, more preferably 0.05 to 3% by weight.
The coloring composition of the present invention may contain only one type or two or more types of organic carboxylic acids and / or organic carboxylic anhydrides. When two or more types are included, the total amount is preferably within the above range.

In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the coloring composition as necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein.
The coloring composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the publication.

<Method for preparing colored composition>
The coloring composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored composition, the components constituting the colored composition may be mixed together, or may be sequentially added 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. If it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, fluorine resins such as PTFE (polytetrafluoroethylene), 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. .
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.

  The colored composition of the present invention can be suitably used for forming a colored layer of a color filter because it can form a cured film having good light resistance, color transfer and flatness. Further, the colored composition of the present invention is a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS (Complementary Metal-Oxide Semiconductor), etc.) or an image display device such as a liquid crystal display device (LCD). It can be suitably used for forming. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably for manufacture of the color filter for solid-state image sensors, such as CCD and CMOS.

<Curing Film, Color Filter, and Color Filter Manufacturing Method>
Next, the cured film and the color filter in the present invention will be described in detail through the manufacturing method. A method for producing the color filter of the present invention will also be described.
The cured film of the present invention is obtained by curing the colored composition of the present invention. Such a cured film is preferably used for a color filter. That is, the color filter of the present invention uses a colored composition.

The first aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer, and a step of exposing the colored composition layer in a pattern. And a step of developing and removing an unexposed portion of the exposed colored composition layer 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. Hereinafter, these steps may be collectively referred to as a pattern forming step.
The second aspect of the method for producing a color filter of the present invention is a step of applying a colored composition of the present invention on a support to form a colored composition layer and curing to form a colored layer, coloring Forming a photoresist layer on the layer, patterning the photoresist layer by exposing and developing the photoresist layer to obtain a resist pattern, and dry etching the colored layer using the resist pattern as an etching mask .
The color filter of the present invention can be suitably obtained by the above production method. These details are described below.

<< 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 a support that can be used in this step, for example, a solid-state imaging element substrate in which an imaging element (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
The colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light shielding film may be provided between the colored patterns in the solid-state image sensor or on the back surface of the substrate for the solid-state image sensor.
Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the colored composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  The coloring composition layer coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

<< When pattern is formed by photolithography >>
<<< Exposure process >>>
In the exposure step, the colored composition layer formed in the colored composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. Thereby, a cured film is obtained.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is preferably ^{30mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 being most preferred.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm.
It is preferable to set the film thickness to 1.0 μm or less because high resolution and high adhesion can be obtained.
In addition, in this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed, and the obtained cured film is developed in a pattern forming process described later, thereby forming a thin film. Although it exists, the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.

<<< Pattern formation process >>>
Next, by performing an alkali development treatment, the colored composition layer of the light non-irradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001% by mass to 10% by mass, An alkaline aqueous solution diluted with pure water so as to be preferably 0.01% by mass to 1% by mass is preferably used as the developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolor coloring pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

<< When pattern is formed by dry etching method >>
Dry etching can be performed by using an etching gas for the colored layer with the patterned photoresist layer as a mask. Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming the photoresist layer, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type radiation sensitive composition is used. The positive type radiation sensitive composition includes a positive type photoresist which is sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer laser, electron beams, ion beams and X rays. A positive resist composition suitable for use can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolving power, it is used for manufacturing integrated circuits such as IC (Integrated Circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products include “FHi622BC” (manufactured by FUJIFILM Electronics Materials).

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm. In addition, the application of the photoresist layer can be suitably performed using the above-described application method in the colored layer.

  Next, by exposing and developing the photoresist layer, a resist pattern (patterned photoresist layer) provided with a group of resist through holes is formed. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the colored layer.

  The exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

  Any developer can be used as long as it does not affect the colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various organic solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

  Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that the through hole group is formed in the colored layer. Thereby, a colored pattern is formed. The through hole group is provided in a checkered pattern in the colored layer. Therefore, the first colored pattern in which the through hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkered pattern.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first-stage etching is performed according to the etching time calculated in (2) above.
(4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.

The mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed. Further, in the second stage etching process and the over etching process, after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.

  Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

  Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.

  Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

  Examples of the process of removing the resist pattern using the cleaning water include a process of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.

  The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine, etc. Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

  The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably contains at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with a stripping solution, it is sufficient that the resist pattern formed on the colored pattern has been removed, and even when the deposit is an etching product on the side wall of the colored pattern, the deposit is completely removed. It may not be removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

  The manufacturing method of the color filter of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as a process other than the above as needed. For example, after performing the coloring composition layer forming step, the exposure step, and the pattern forming step described above, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.

In addition, the solvent for the colored composition of the present invention is used to efficiently clean the nozzles and pipes of the discharge unit of the coating apparatus, contamination due to adhesion, sedimentation, and drying of the colored composition and pigment in the coating machine. Is preferably used as the cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can be suitably used.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid to contaminants, the above-described surfactant relating to the colored composition of the present invention may be added to the cleaning liquid.

Since the color filter of the present invention uses the colored composition of the present invention, the color filter is excellent in light resistance, color transfer and flatness.
The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the color filter of the present invention described above or the color filter manufactured by the method for manufacturing the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

On the support, there are a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon, etc., and the photodiode is placed on the transfer electrode. A light-shielding film made of tungsten or the like that is open only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. Further, the color filter for a solid-state image sensor according to the present invention is provided.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light condensing means on the color filter, etc. It may be.

<Image display device>
The color filter of the present invention described above or the color filter manufactured by the method of manufacturing the color filter of the present invention is not limited to a solid-state image sensor, but an image such as a liquid crystal display device or an organic EL (Electro-Luminescence) display device. It can be used for a display device and is particularly suitable for a liquid crystal display device. 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.

  For the definition of display devices and details of each display device, for example, “Electronic display devices (Akio Sasaki, published by the Industrial Research Council 1990)”, “Display devices (written by Junaki Ibuki, published in 1989, Industrial Books)”, etc. It is described in. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Committee 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 may be used in 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 Kyoritsu Publishing 1996)”. 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), and a STN (Super-twisted nematic). ), TN (Twisted Nematic), VA (Vertically Aligned), OCS (Optically Compensated Splay), FFS (Fringe Field Switching), and R-OCB (Optically Compensated Bend).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. In the color filter of the present invention, since a dye having excellent hue is used, the color purity, light transmittance, etc. are good and the color of the colored pattern (pixel) is excellent. Therefore, the COA method has high resolution and excellent long-term durability. A liquid crystal display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP (Plasma Display Panel), LCD Display-Latest Technology and Market Trends-(Toray Research Center Research and Research Division 2001 Issue)" Yes.

In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. As for these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Omoyoshi Yoshi Fuji Chimera Research Institute, Issued in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Have been described.
Further, in the present invention, it can be preferably used for a display of micro O red type (micro OLED (Organic light-emitting diodes). For example, “EL, PDP, LCD display technology and market”. Page 43, etc. of “Latest Trends in Toray Research Center (issued in 2001)”.

  When the color filter according to the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green, and blue LED light sources (RGB (Red Green By using Blue) -LED) as a backlight, it is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Unless otherwise specified, “%” and “parts” are based on mass.

<Measurement method of weight average molecular weight>
The weight average molecular weight was measured in terms of polystyrene by GPC (Gel Permeation Chromatography) measurement. Specifically, HLC-8220 (manufactured by Tosoh) was used, TSKgel Super AWM-H (manufactured by Tosoh, 6.0 mm ID × 15.0 cm) was used as a column, and 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) was used as an eluent. ) By using the solution.

<Method for measuring acid value>
The acid value represents the weight of potassium hydroxide required to neutralize acidic components per gram of solid content. Specifically, the measurement sample was dissolved in a tetrahydrofuran / water = 9/1 mixed solvent, and the obtained solution was used at 25 ° C. using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry). Neutralization titration with 0.1M aqueous sodium hydroxide was performed. The acid value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 M sodium hydroxide aqueous solution required for titration (mL)
f: Potency of 0.1 M aqueous sodium hydroxide solution w: Weight of measurement sample (g) (converted to solid content)

<Measurement of absorbance>
Absorbance at 25 ° C. was measured with a UV-Vis-NIR spectrophotometer (trade name: Cary 5000, manufactured by Agilent Technologies, Inc.) using a cell having an optical path length of 1 cm.

<Synthesis Example of Triarylmethane Dye (A-tp-1), (A-tp-3), (A-tp-5), (A-tp-8)>
Triarylmethane dyes (A-tp-1) and (A-tp-3) in the same manner as described in paragraphs 0112 to 0114 of JP-A No. 2000-162429 (Example 4 (Compound Formula 2)) , (A-tp-5) and (A-tp-8) were synthesized.

<Synthesis Example of Xanthene Compound (A-xt-104)>

<< Synthesis of Intermediate 1 >>
DCSF (Spiro [3H-2,1-benzoxathiole-3,9 '-[9H] xanthene], 3', 6'-dichloro-, 1,1-dioxide, manufactured by Chugai Kasei) 31 parts, 2,6-diisopropyl 67 parts of aniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask and stirred at an external temperature of 200 ° C. for 8 hours. Thereafter, the mixture was allowed to cool to room temperature, the reaction solution was added dropwise to 600 parts of 2N aqueous hydrochloric acid, and the precipitated crystals were filtered off. The crystals were dispersed and washed with 600 parts of acetonitrile at 40 degrees, and then collected by filtration and air-dried for 10 hours to obtain 42.5 parts of intermediate 1 (yield: 82%).

<< Synthesis of Intermediate 2 >>
11 parts of Intermediate 1 and 50 parts of phosphorus oxychloride (POCl ₃ ) were placed in a flask and stirred at 60 ° C. for 4 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added dropwise to 150 parts of ice water and stirred for 30 minutes. The obtained crystals were separated by filtration and washed with 20 parts of water, and then the obtained crystals were dissolved in 150 parts of chloroform and filtered through celite. The filtrate was separated and washed with 100 parts of 5% brine and 100 parts of 15% brine. After drying sodium sulfate, the solution was concentrated under reduced pressure to obtain 12.1 parts of intermediate 2 (yield: 91%).

<< Synthesis of Intermediate 3 >>
15 parts of pentafluorobenzenesulfonyl chloride and 300 parts of tetrahydrofuran (THF) were placed in a flask, and the internal temperature was cooled to -10 ° C. Thereto, 6.8 parts of 28% aqueous ammonia (NH ₃ aq) was added dropwise so that the reaction solution maintained at 0 ° C. or lower. After dropping, the reaction solution was filtered after stirring at 0 ° C. for 1 hour. The obtained filtrate was concentrated under reduced pressure to remove THF, and then 100 parts of water was added and stirred. The obtained solid was filtered, washed with water, and then air-dried for 10 hours to obtain 11.7 parts of intermediate 3 (yield: 84%).

<< Synthesis of Intermediate 4 >>
15 parts of Intermediate 3, 4.9 parts of 2-mercaptoethanol, and 100 parts of methanol were added to the flask and stirred at room temperature. Thereto, 6.5 parts of triethylamine (TEA) was added dropwise so that the temperature of the reaction solution did not exceed 30 ° C. After stirring at room temperature for 1 hour and concentrating under reduced pressure, 90 parts of ethyl acetate, 80 parts of saturated brine, and 10 parts of saturated aqueous sodium bicarbonate were added to carry out a liquid separation operation. After extracting the aqueous layer with 90 parts of ethyl acetate, magnesium sulfate was added to the obtained organic layer. After filtration, the filtrate was concentrated under reduced pressure and air-dried for 10 hours to obtain 17 parts of intermediate 4 (yield: 92%).

<< Synthesis of Intermediate 5 >>
49 parts of Intermediate 4 25 parts of 2-isocyanatoethyl acrylate (AOI, Showa Denko), 0.2 parts of dibutylhydroxytoluene (BHT), 95 parts of dimethylacetamide (DMAc), Neostan U-600 (manufactured by Nitto Kasei) ) 0.1 part was added to the flask and stirred at 85 ° C. for 1 hour. Subsequently, 500 parts of ethyl acetate and 500 parts of saturated brine were added to carry out a liquid separation operation. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure. The obtained solid was suspended and washed with 170 parts of chloroform, filtered, and blown and dried to obtain 60 parts of intermediate 5 (yield: 84%).

<< Synthesis of Xanthene Compound (A-xt-104) >>
5 parts of Intermediate 5, 50 parts of methylene chloride and 3.4 parts of triethylamine (TEA) were added to the flask and stirred at room temperature. Thereto was added 10.8 parts of Intermediate 2 and stirred at room temperature for 2 hours. After completion of the reaction, 200 parts of chloroform, 500 parts of pure water and 200 parts of saturated saline were added to carry out a liquid separation operation. Sodium sulfate was added to the obtained organic layer and dehydrated, followed by filtration, and the filtrate was concentrated under reduced pressure. The obtained solid was dissolved in chloroform and purified by column chromatography using a chloroform / ethyl acetate solvent to obtain 12.5 parts (yield: 86%) of A-xt-104.

<Synthesis Example of Xanthene Compounds (A-xt-101), (A-xt-110), (A-xt-117), (A-xt-118)>
Xanthene compounds (A-xt-101), (A-xt-110), (A-xt-117), and (A-xt-118) were synthesized in the same manner as the xanthene compound (A-xt-104). .

<Synthesis example of thiol compound>
As shown below, thiol compounds B-1 to B-12 were synthesized.

[Synthesis Example B-1]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by SC Organic Chemical Industry] 2.0 parts, 12.0 parts of triarylmethane dye (A-tp-1), 1.68 parts of triethylamine Was dissolved in 50.0 parts of N-methylpyrrolidinone (NMP) and heated at 50 ° C. for 12 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and reprecipitated to obtain 12.5 parts of a thiol compound (B-1) shown below. It was confirmed that the ratio of the dye moiety to the R ³ moiety in the NMR measurement was 5.

[Synthesis Example B-2]
In Synthesis Example B-1, 12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine, 9.6 parts of triarylmethane dye (A-tp-1), and 1. 10.5 parts of thiol compound (B-2) were obtained like synthesis example B-1 except having changed to 34 parts. It was confirmed that the ratio of the dye moiety to the R ³ moiety in the NMR measurement was 4.

[Synthesis Example B-3]
In Synthesis Example B-1, 12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine, 7.2 parts of triarylmethane dye (A-tp-1), and 1. 8.3 parts of thiol compound (B-3) was obtained in the same manner as in Synthesis Example B-1, except that the amount was changed to 01 parts. It was confirmed that the ratio of the dye moiety to the R ³ moiety in the NMR measurement was 3.

[Synthesis Example B-4]
In Synthesis Example B-1, 12.0 parts of triarylmethane dye (A-tp-1) and 1.68 parts of triethylamine, 4.8 parts of triarylmethane dye (A-tp-1), and 0. Except having changed to 67 parts, it carried out similarly to the synthesis example B-1, and obtained 6.0 parts of thiol compounds (B-4). It was confirmed that the ratio of the dye moiety to the R ³ moiety in the NMR measurement was 2.

[Synthesis Example B-5]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by SC Organic Chemical Industry] 2.0 parts, triarylmethane dye (A-tp-3) 11.6 parts, triethylamine 0.21 parts , Dissolved in 50.0 parts of N-methylpyrrolidinone (NMP) and heated at 50 ° C. for 12 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and reprecipitated to obtain 12.3 parts of a thiol compound (B-5).

[Synthesis Example B-6]
2.0 parts of dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by SC Organic Chemical Industry] and 9.4 parts of triarylmethane dye (A-tp-8) were mixed with N-methylpyrrolidinone ( NMP) was dissolved in 50.0 parts and heated to 80 ° C. in a nitrogen atmosphere. After adding 0.13 part of 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries, Ltd.], the mixture was heated and stirred at 80 ° C. for 2 hours. Further, 0.13 part of V-601 was added, and the mixture was stirred with heating at 80 ° C. for 2 hours, and then cooled to room temperature. The reaction solution was dropped into a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and reprecipitated to obtain 10.2 parts of a thiol compound (B-6).

[Synthesis Example B-7]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by SC Organic Chemical Industry] in Synthesis Example B-1 2.0 parts, 12.0 parts of triarylmethane dye (A-tp-1), triethylamine 1.68 parts, pentaerythritol tetra (3-mercaptopropionate) [PEMP; manufactured by SC Organic Chemical Industry] 2.0 parts, xanthene compound (A-xt-101) 9.9 parts, triethylamine 1.62 parts 10.7 parts of a thiol compound (B-7) was obtained in the same manner as in Synthesis Example B-1, except that it was changed to.

[Synthesis Example B-8]
In Synthesis Example B-5, 11.6 parts of triarylmethane dye (A-tp-3) and 0.21 part of triethylamine, 14.2 parts of xanthene compound (A-xt-104), and 0.26 part of triethylamine 14.4 parts of thiol compound (B-8) was obtained in the same manner as in Synthesis Example B-5, except that

[Synthesis Example B-9]
In Synthesis Example B-5, 11.6 parts of triarylmethane dye (A-tp-3) and 0.21 part of triethylamine, 11.4 parts of xanthene compound (A-xt-104), and 0.21 part of triethylamine Except for changing to, 12.1 parts of thiol compound (B-9) was obtained in the same manner as in Synthesis Example B-5.

[Synthesis Example B-10]
In Synthesis Example B-5, 11.6 parts of triarylmethane dye (A-tp-3) and 0.21 part of triethylamine, 8.6 parts of xanthene compound (A-xt-104), and 0.16 part of triethylamine 9.5 parts of thiol compound (B-10) was obtained in the same manner as in Synthesis Example B-5 except that the thiol compound (B-10) was changed.

[Synthesis Example B-11]
The same as Synthesis Example B-6, except that 9.4 parts of triarylmethane dye (A-tp-8) in Synthesis Example B-6 was changed to 4.2 parts of squarylium compound (Ak-1). As a result, 5.6 parts of a thiol compound (B-11) was obtained.

[Synthesis Example B-12]
The same as Synthesis Example B-6 except that 9.4 parts of triarylmethane dye (A-tp-8) in Synthesis Example B-6 was changed to 4.2 parts of cyanine compound (A-pm-1) Thus, 5.6 parts of a thiol compound (B-12) was obtained.

<Synthesis of a dispersant having a dye structure>
[Synthesis Example C-1]
A mixed solution of 5.0 parts of the thiol compound (B-1) obtained in Synthesis Example B-1, 0.96 parts of methacrylic acid (MAA), and 9.0 parts of cyclohexanone was heated to 80 ° C. in a nitrogen stream. 0.077 part of 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries, Ltd.] was added thereto, and the mixture was heated and stirred at 80 ° C. for 2 hours. Further, 0.077 part of V-601 was added, and the mixture was heated and stirred at 80 ° C. for 2 hours, and further stirred at 90 ° C. for 2 hours. After cooling to room temperature, 30.7 parts of cyclohexanone, 0.14 part of tetrabutylammonium bromide (TBAB) and 0.79 part of glycidyl methacrylate (GMA) were added and stirred with heating at 80 ° C. for 18 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 250 parts of hexane and 250 parts of ethyl acetate and reprecipitated to obtain a dispersant (C-1) having the following dye structure. The weight average molecular weight (polystyrene conversion value) of the dispersant (C-1) having a dye structure was 11600, and the acid value was 46 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution. From the NMR, the molar ratio of the adduct of dye structure / MAA / MAA and GMA was calculated to be 5/6/6, and the average number of repetitions of the P part was 12. Further, a solution containing 0.01 mg / ml of the dispersant (C-1) having a dye structure dissolved in tetrahydrofuran (THF) is prepared (concentration adjusted so that the maximum absorbance is 1.0), and the solution The absorbance at 25 ° C. was measured using a cell having an optical path length of 1 cm. As a result, the maximum absorption wavelength (λmax) was 615 nm, and the specific absorbance at the maximum absorption wavelength (λmax) was 60.

[Synthesis Examples C-2 to 12]
It has a dye structure in the same manner as in Synthesis Example C-1, except that the amount of thiol compound, polymerizable monomer, amount of V-601, amount of glycidyl methacrylate, and amount of tetrabutylammonium bromide are changed to Table 1 below. Dispersants (C-2) to (C-12) were obtained.

<Measurement of specific absorbance>
Each dye is dissolved in tetrahydrofuran (THF) to adjust the concentration so that the maximum absorbance at a wavelength of 400 nm to 800 nm is 1.0, and the absorbance at 25 ° C. of the solution is as follows using a cell having an optical path length of 1 cm. Calculation was performed based on the formula (Aλ).
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of the dye in the solution expressed in mg / ml.

[Synthesis Example C-13]
A mixed solution of 5.0 parts of the thiol compound (B-1) obtained in Synthesis Example B-1, 0.96 parts of methacrylic acid (MAA), 10.0 parts of methyl methacrylate and 19.5 parts of N-ethylpyrrolidone. It heated at 90 degreeC under nitrogen stream. To this was added 0.77 part of 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries, Ltd.], and the mixture was heated and stirred at 90 ° C. for 1.5 hours. Further, 0.77 part of V-601 was added, followed by heating and stirring at 90 ° C. for 1.5 hours, and further heating and stirring at 90 ° C. for 2 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 500 mL of hexane and 500 mL of ethyl acetate and reprecipitated to obtain a dispersant (C-13) having the following dye structure. The weight average molecular weight (polystyrene conversion value) of the dispersant (C-13) having a dye structure was 27500, and the acid value was 39 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution. From the NMR, the molar ratio of dye structure / MAA / MMA was 5/12/108. Further, a solution containing 0.01 mg / ml of the dye (C-45) was prepared by dissolving in tetrahydrofuran (THF), and the absorbance of the solution at 25 ° C. was measured using a cell having an optical path length of 1 cm. The maximum absorption wavelength (λmax) was 615 nm, and the specific absorbance at the maximum absorption wavelength (λmax) was 25.

[Synthesis Examples C-14 to 24]
Dispersants C-14 to C having a dye structure in the same manner as in Synthesis Example C-13, except that the amount of the thiol compound, the polymerizable monomer, and the amount of the photopolymerization initiator are changed to those described in Table 2 below. -24 was obtained.

The types of polymerizable monomers described in Tables 1 and 2 are shown below.

  Using a triarylmethane dye (A-tp-1) as a dye, a dispersant D-1 having a dye structure having the structure shown below was synthesized. Detailed operations will be described below.

<Synthesis of Macromonomer (N-1)>
Under a nitrogen atmosphere, 35.0 g (0.27 mol) of 2-ethylhexanol, 307.1 g (2.70 mol) of ε-caprolactone and 0.20 g of monobutyltin oxide were heated at 90 ° C. for 5 hours and subsequently at 110 ° C. for 10 hours. A polyester monohydroxy product was obtained. The completion of the reaction was confirmed by measuring the disappearance of ε-caprolactone by NMR. After cooling to 80 ° C., 0.071 g of 2,6-ditertiarybutyl-4-methylphenol and 42.3 g (0.27 mol) of 2-methacryloyloxyethyl isocyanate were added, and the reaction was performed at 80 ° C. for 3 hours. Monomer N-1 was obtained. The completion of the reaction was confirmed by measuring the disappearance of 2-methacryloyloxyethyl isocyanate by NMR. The weight average molecular weight of the macromonomer N-1 determined by GPC was 2200.
[Synthesis Example D-1]

A triarylmethane dye (A-tp-101) was synthesized according to the method described in JP-A No. 2000-162429.
Triarylmethane dye (A-tp-101) (15 g), macromonomer N-1 (12 g), and methacrylic acid (3.5 g) were dissolved in dodecanethiol (0.75 g) and stirred at 80 ° C. After adding 1.70 parts of 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries, Ltd.], the mixture was heated and stirred at 80 ° C. for 2 hours. Further, 1.70 parts of V-601 were added, and then heated and stirred at 80 ° C. for 2 hours, and further heated and stirred at 90 ° C. for 2 hours. After cooling to room temperature, the reaction solution was dropped into a mixed solvent of 500 mL of hexane and 500 mL of ethyl acetate and reprecipitated to obtain a dispersant (D-1) having a dye structure. The weight average molecular weight (polystyrene conversion value) of the dispersant (D-1) having a dye structure was 7400, and the acid value was 110 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution. From the NMR, the molar ratio of the dye structure / N-1 / MMA was 10/74/16. Further, a solution containing 0.01 mg / ml of the dye (D-1) was prepared by dissolving in tetrahydrofuran (THF), and the absorbance of the solution at 25 ° C. was measured using a cell having an optical path length of 1 cm. The maximum absorption wavelength (λmax) was 615 nm, and the specific absorbance at the maximum absorption wavelength (λmax) was 20.

[Synthesis Examples D-2 to 16]
Dispersant D-2 having a dye structure in the same manner as in Synthesis Example D-1, except that the amount of the dye monomer, other polymerizable monomer, V-601 and the amount of dodecanethiol were changed to those shown in Table 3 below. ~ D-16 was obtained. N-2 is AA-6 (macromonomer manufactured by Toa Gosei). A-pm-2 and Ak-2 represent compounds having the following structures.

Comparative dye 1: Triarylmethane dye (A-tp-1): The following structure comparison dye 2: Xanthene compound (A-xt-105): The following structure

(Synthesis of Comparative Dispersants 4-6)
Comparative dyes 4 to 6 having the structural formula shown below were synthesized by the method described in paragraph Nos. 0272 to 0326 of JP-A-2007-277514. Comparative dispersant 4: the following structure (Synthesis Example C-9 of JP-A-2007-277514)
In the formula, m = 1, n = 5 Comparative dispersant 5 The following structure (Synthesis Example C-25 of JP 2007-277514 A)
In the formula, m = 1, n = 3 Comparative dispersant 6 The following structure (Synthesis Example C-4 of JP 2007-277514 A)
In the formula, m = 1, n = 5 Comparative dispersant 4
Comparative dispersant 5
Comparative dispersant 6

(Synthesis of Comparative Dispersant 7)
Comparative dye 7 having the structural formula shown below was synthesized by the method described in paragraph No. 0136 of JP2011-1118060A. That is, 2 g of methacrylic acid, 8.3 g of a macromonomer (manufactured by Toagosei Co., Ltd., AA-6), 2.6 g of a monomer a having the dipyrromethene dye skeleton (the following structure), 30 g of propylene glycol methyl ether acetate, and 1-dodecanethiol 2 g was stirred under nitrogen and kept at 75 ° C. Next, 0.06 part of photopolymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred for 2 hours. Stir at 90 ° C. for 2 hours. After cooling to room temperature, a dispersant having a dye structure (Comparative Dye 7) was obtained. The weight average molecular weight (polystyrene conversion value) of the comparative dye 7 was 12000, and the acid value was 100 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution. Further, a solution containing 0.01 mg / ml of the dye (D-1) was prepared by dissolving in tetrahydrofuran (THF), and the absorbance of the solution at 25 ° C. was measured using a cell having an optical path length of 1 cm. The maximum absorption wavelength (λmax) was 550 nm, and the specific absorbance at the maximum absorption wavelength (λmax) was 18.
Monomer a having a dipyrromethene dye skeleton

<Example 1>
1. Preparation of resist solution Components of the following composition were mixed and dissolved to prepare an undercoat layer resist solution.
Composition of resist solution for undercoat layer: Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (Molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) 40% PGMEA solution 30.51 parts ethylenically unsaturated double bond-containing compound: dipentaerythritol hexaacrylate, KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 12.20 parts ・ Polymerization inhibitor: p-methoxyphenol 0.0061 parts ・ Fluorosurfactant: F-475, DIC 0.83 parts ・ Photopolymerization initiator: Trihalomethyl Triazine-based photopolymerization initiator 0.586 parts (TAZ-107, Midori Made Manabu)

2. Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, an undercoat layer resist solution is applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate was obtained.

3. Preparation of coloring composition 3-1. Preparation of Blue Pigment Dispersion <Preparation of Pigment Dispersion P-1 (CI Pigment Blue 15: 6 Dispersion)>
A pigment dispersion P-1 (CI Pigment Blue 15: 6 dispersion) was prepared as follows.
That is, C.I. I. Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle diameter 55 nm), Dispersant C-1 having a dye structure 20.95 parts by mass, PGMEA275 The mixed liquid consisting of parts by mass was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter). Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained. The obtained C.I. I. With respect to Pigment Blue 15: 6 dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 28 nm.

<Preparation of Pigment Dispersions P-2 to P-42 and Comparative Dispersions P-1 to P-7>
In the preparation of pigment dispersion P-1, pigment dispersions P-2 to P-42 and comparative dispersions were prepared in the same manner except that the dispersants or pigments having a pigment and a dye structure were used as shown in Table 4 below. P-1 to P-7 were prepared.
PR is C.I. I. Pigment Red, PG is C.I. I. It means pigment green.
The comparative dispersion P-3 does not contain a dispersant having a dye structure and a comparative dye.

<Preparation of Pigment Dispersion Liquid P-43>
A pigment dispersion P-43 (CI Pigment Blue 15: 6 dispersion) was prepared as follows.
That is, C.I. I. Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as “PB15: 6”) 24.56 parts by mass (average primary particle diameter 55 nm), and Dispersant C-1 having a dye structure 12.28 parts by mass, dye A mixed liquid consisting of 3.51 parts of pigment dispersant BY-161 (manufactured by BYK) having no structure and 275 parts by mass of PGMEA was mixed and dispersed by a bead mill (zirconia beads 0.3 mm diameter) for 3 hours. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained. The obtained C.I. I. With respect to Pigment Blue 15: 6 dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 32 nm.

<Preparation of pigment dispersion P-44>
In the preparation of Pigment Dispersion Liquid P-43, Pigment Dispersion Liquid P was prepared in the same manner except that the dispersant having the dye structure was changed to D-8 and the pigment dispersant not having the dye structure was changed to E1 (the following structure). -44 was prepared.

Mw = 20000, x / y = 50/50 (mass ratio), n = 20, acid value = 100 mgKOH / g

3-2. Preparation of colored composition The following components were mixed, dispersed and dissolved, and filtered through a 0.45 µm nylon filter to obtain a colored composition. The ratio (unit) of the pigment in the solid content is 33%, and the ratio of the dispersant is 36%.
Organic solvent (cyclohexanone): 17.12 parts Alkali-soluble resin 1 (J1 below): 1.23 parts (solid content 0.37 parts, solid content concentration 30%)
Alkali-soluble resin 2 (Acryl Cure-RD-F8 (manufactured by Nippon Shokubai)): 0.23 part Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 part Pigment dispersion P-1 (C Pigment Blue 15: 6 and Dispersant C-1 dispersion, PGMEA solution, solid concentration 12.8%): 61.50 parts Polymerizable compound Z-1 (ethyleneoxy-modified dipentaerythritol hexaacrylate, NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)): 1.96 parts ・ Polymerization inhibitor (p-methoxyphenol): 0.0007 parts ・ Fluorosurfactant (DIC F475, 1% PGMEA solution) : 2.50 parts

Alkali-soluble resin J1

4). Production of color filter (colored pattern) 4-1: Production of color filter using colored composition by photolithography method The colored composition prepared above is applied to the undercoat layer of the silicon wafer with an undercoat layer prepared above. To form a colored layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 1 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon), exposure was performed at an exposure dose of 50 to 1200 mJ / cm ² through an island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Materials). Was used for 60 seconds at 23 ° C. to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.
The silicon wafer on which the colored pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is sprayed from the jet nozzle from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. After being supplied and rinsed, it was spray-dried and post-baked with a hot plate at 200 ° C. for 300 seconds to obtain a colored pattern (color filter) having a thickness of 1 μm on the silicon wafer.
As described above, a silicon wafer with a colored pattern having a structure in which a colored pattern (color filter) was provided on the undercoat layer of the silicon wafer with an undercoat layer was obtained.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies).
The development residue was evaluated using a colored pattern having an exposure amount of 1.0 μm in pattern size.

<Evaluation of development residue>
The outside of the colored pattern formation region (unexposed portion) on the silicon wafer was observed at a magnification of 30000 using a scanning electron microscope, and evaluated according to the following evaluation criteria.
A Good: No residue was observed outside the colored pattern forming area (unexposed area).
B Slightly good: Although a slight residue was observed outside the colored pattern formation region (unexposed area), there was no practical problem.
C sufficient: Residue was confirmed outside the colored pattern formation region (unexposed portion). By changing the development condition from paddle development at 23 ° C. for 60 seconds to paddle development at 23 ° C. for 180 seconds, there was no practical problem.
D insufficient: Residue was remarkably confirmed outside the colored pattern formation region (unexposed portion). Further, even if the development condition was changed from paddle development at 23 ° C. for 60 seconds to paddle development at 23 ° C. for 180 seconds, residues were confirmed, and there was a practical problem.

<Color loss>
On the glass substrate, the coloring composition was applied using a spin coater so as to have a film thickness of 0.6 μm, and heat-treated (prebaked) for 120 seconds using a hot plate at 100 ° C. Next, heat treatment (post-bake) was performed for 300 seconds using a 220 ° C. hot plate to prepare a cured film.
The transmittance of the color filter thus obtained was measured in a wavelength region of 300 nm to 800 nm with a spectrophotometer (reference: glass substrate) of an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation). Moreover, the differential interference image was observed by reflection observation (50-times multiplication factor) using OLYMPUS optical microscope BX60.
Next, the specimen was immersed in an alkali developer FHD-5 (manufactured by Fuji Film Electronics Materials) for 5 minutes, dried, and then subjected to spectroscopic measurement again. The transmittance fluctuation before and after the solvent immersion (the above-mentioned transmittance before the solvent immersion). Is T0, and the transmittance after immersion in the solvent is T1, the value represented by the expression | T0-T1 |) and the film surface abnormality were evaluated, and evaluated according to the following criteria.
<< Evaluation criteria >>
A: Good The transmittance variation before and after immersion in the solvent is less than 2% in the entire region of 300 nm to 800 nm. B: Slightly good In the entire region of 300 nm to 800 nm, the transmittance variation before and after the solvent immersion is 2% or more and less than 5%. Sufficient fluctuation in transmittance before and after solvent immersion in the entire region of 300 nm to 800 nm is 5% or more and less than 10% D: Inadequate transmittance fluctuation in the entire region of 300 nm to 800 nm is 10% or more

<Light resistance>
The colored composition prepared above was applied to a glass substrate using a spin coater (manufactured by Mikasa) to form a coating film. And heat processing (prebaking) was performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.6 micrometer. Next, heating was performed at 200 ° C. for 5 minutes, and the coating film was cured to form a colored layer.
Using a light resistance test apparatus (SX-75 manufactured by Suga Test Instruments Co., Ltd.), the glass substrate on which the colored layer was formed was black panel temperature 63 ° C., quartz inner filter, 275 nm cut outer filter, illuminance 75 mw / m ² (300 to 400 nm), humidity Heated for 10 hours under 50% condition.
The color difference (ΔE * ab) before and after heating was measured with a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics). Based on the measured color difference (ΔE * ab), light resistance was evaluated according to the following evaluation criteria. It can be said that the smaller this value, the better the light resistance. The evaluation results are shown in the following table. A and B are levels at which there is no problem in actual use.

<< Evaluation criteria >>
A Good: ΔE * ab is 3 or less B Good: ΔE * ab is greater than 3 and 5 or less C Sufficient: ΔE * ab is greater than 5 and 10 or less D Insufficient: ΔE * ab is greater than 10

<Zara (color unevenness)>
The obtained monochromatic color filter (colored pattern) is placed between the observation lens and the light source of the optical microscope to irradiate the light toward the observation lens, and a digital camera with a magnification of 1000 times installs the transmitted light state. Was observed with an optical microscope. A digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels, and the surface of the coating film in a transmitted light state was photographed. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format.
In addition, imaging | photography of the coating surface of a coloring pattern was performed with respect to 20 area | regions selected arbitrarily. In addition, the digitally converted data was obtained by digitizing and storing the captured image as a density distribution of 256 gradations in which the brightness of the B color is 0 to 255.
Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged. In this example, since an image of 1000 times optical was captured with a 1.28 million pixel digital camera, 2 μm on the actual substrate was 2 mm on the captured image, and the image size on the display was 452 mm × 352 mm. The total number of sections in one area was 39976.
For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A partition having a difference of 5 or more from the average brightness of adjacent partitions is recognized as a significant difference partition, and the average total number of significant difference partitions in all regions and the average total number of significant difference partitions in all regions are the total number of partitions in each region (39976). The ratio (hereinafter, also simply referred to as “ratio”) to the total number was calculated. It is determined that the smaller this value is, the less color unevenness (zara) is. The number of significant difference sections is 800 or less, and the ratio is 3% or less.

<< Evaluation criteria >>
A: The number of significant difference sections is less than 500 and the ratio is less than 2%, and is excellent. Level B: The number of significant difference sections is 800 or less, and the ratio is 3% or less. Excluded) Level C with no practical problems: Levels that are at least one of the number of significant difference divisions of more than 800 and more than 3%, and levels that are practically problematic, and those that do not fall under A and B above.

<Examples 2-49 and Comparative Examples 1-7>

  In “3-2. Preparation of colored composition” in Example 1, pigment dispersion P-1, photopolymerization initiator I-2, alkali-soluble resin J1, and polymerizable compound Z-1 were changed as shown in the following table. Except for this, a colored composition was prepared in the same manner as in Example 1, and the development residue, color loss, light resistance, and roughness were evaluated in the same manner as in Example 1.

Photopolymerization initiator: Structure below

Alkali-soluble resins J2 to J4: the following structures

J1 acid value: 195 mgKOH / g, J2 acid value: 51 mgKOH / g, J3 acid value: 49 mgKOH / g, J4 acid value: 34 mgKOH / g,

Polymerizable compound Z-1: ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical)
Z-2: Dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku)
Z-3: Ethoxylation (4) Pentaerythritol tetraacrylate, SR494 (manufactured by Sartomer)
Z-4: Ethoxylation (3) Trimethylolpropane triacrylate, SR454 (Sartomer)
Z-5: Ethoxylation (6) Trimethylolpropane triacrylate, SR499 (manufactured by Sartomer)
Z-6: KAYARAD DPCA-60 (Nippon Kayaku)
Z-7: Tris (2-hydroxyethyl) isocyanurate triacrylate, SR368 (manufactured by Sartomer)

From the said table | surface, when the pigment dispersion liquid of the Example was used, it turned out that color loss can be suppressed and light resistance can be improved. It was also found that development residue and roughness can be further reduced.
On the other hand, it was found that when the pigment dispersion of the comparative example was used, it was difficult to achieve both suppression of color loss and improvement of light resistance.

4-2: Preparation and evaluation of color filter by dry etching process (Preparation of coloring composition for dry etching)
The following components were mixed and dispersed and dissolved to obtain a colored composition.
Organic solvent (cyclohexanone): 17.12 parts Epoxy resin JER1031S (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 180-220 (g / eq.)): 4.395 parts Pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion, PGMEA solution, solid content concentration 12.8%): 75.97 parts Polymerization inhibitor (p-methoxyphenol): 0.0007 parts Fluorosurfactant (manufactured by DIC, F475) 1% PGMEA solution): 2.50 parts

(Preparation of color filter using colored curable composition by dry etching method)
The coloring composition for dry etching obtained above was applied on a 7.5 cm × 7.5 cm glass substrate using a spin coater, heated at 200 ° C. for 5 minutes using a hot plate, The coating film was cured to prepare a colored layer. The thickness of this colored layer was 0.5 μm.
Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied and prebaked at 90 ° C. for 1 minute to form a 0.8 μm-thick photoresist layer.
Subsequently, the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) at an exposure amount of 350 mJ / cm ² , and the photoresist layer temperature or ambient temperature was 90 ° C. for 1 minute. The heat treatment was performed. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern. The resist pattern was formed with a side of 1.0 μm in consideration of etching conversion difference (pattern width reduction by etching).
Next, the obtained glass substrate was attached to an 8-inch silicon wafer, and RF (Radio Frequency) power: 800 W, antenna bias: 400 W, wafer bias using a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation). : 200 W, internal pressure of the chamber: 4.0 Pa, substrate temperature: 50 ° C., gas species and flow rate of the mixed gas are CF ₄ : 80 mL / min, O ₂ : 40 mL / min, Ar: 800 mL / min. As a result, the first stage etching process of 80 seconds was performed.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N ₂ : 500 mL / min, O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10), and the second-stage etching treatment and over-etching treatment for 28 seconds were performed.
After performing dry etching under the above conditions, a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used to perform a stripping process at 50 ° C. for 120 seconds to remove the resist, and it is colored blue A pattern was formed. Further, washing with pure water and spin drying were performed, and then a dehydration baking process was performed at 100 ° C. for 2 minutes. As a result, a color filter was obtained.

<Evaluation of development residue>
The outside of the colored pattern formation region (unexposed portion) on the silicon wafer was observed at a magnification of 30000 using a scanning electron microscope, and evaluated according to the following evaluation criteria. As a result, no residue was observed outside the colored pattern formation region (unexposed portion), which was good.

<Evaluation of anti-color loss>
Color loss resistance was evaluated in the same manner as in the production of a color filter using a colored composition by the photolithography method. As a result, in the entire region of 300 nm to 800 nm, the transmittance fluctuation before and after immersion in the solvent was less than 2%, which was good.

<Evaluation of light resistance>
The light resistance was evaluated in the same manner as in the production of a color filter using the colored composition by the photolithography method. As a result, ΔE * ab was 3 or less, which was good.

<Evaluation of zara (color unevenness)>
The roughness (color unevenness) was evaluated in the same manner as in the production of the color filter using the colored composition by the photolithography method. As a result, the number of significant difference sections was less than 500, and the ratio was less than 2%, which was an excellent level.

Claims (9)

Including dispersing the pigment in the presence of a dispersant having a dye structure;
The dispersant having the dye structure has a dye structure selected from a triarylmethane dye, a xanthene dye, a cyanine dye and a squarylium dye;
The dispersant having the dye structure is a dye multimer having two or more of the dye structures in the same molecule, and the specific absorbance represented by the following formula (Aλ) at the maximum absorption wavelength at 400 nm to 800 nm is 5 or more. A method for producing a pigment dispersion;
E = A / (c × l) (Aλ)
In the formula (Aλ), E represents the specific absorbance at the maximum absorption wavelength at 400 nm to 800 nm,
A represents the absorbance at the maximum absorption wavelength between 400 nm and 800 nm,
l represents the cell length in units of cm;
c represents the concentration of a dispersant having a dye structure in a solution, the unit of which is expressed in mg / ml. The dye structure of the dispersant having the dye structure includes an anion moiety, and the anion moiety is a sulfonate anion, a carboxylate anion, a tetraarylborate anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , and the following general formula ( The production of a pigment dispersion according to claim 1, which is at least one selected from the group consisting of a group containing a structure represented by A1) and a group containing a structure represented by the following general formula (A2). Method;
General formula (A1)
In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—;
General formula (A2)
In general formula (A2), R ³ represents —SO ₂ — or —CO—; R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN. The manufacturing method of the pigment dispersion liquid of Claim 1 or 2 which uses 80-150 mass parts of pigments with respect to 100 mass parts of dispersing agents which have the said pigment | dye structure. The manufacturing method of the pigment dispersion liquid of any one of Claims 1-3 whose weight average molecular weights of the dispersing agent which has the said pigment | dye structure are 3000 or more and 50000 or less. The manufacturing method of the pigment dispersion liquid of any one of Claims 1-4 whose acid value of the dispersing agent which has the said pigment | dye structure is 27 mgKOH / g or more and less than 200 mgKOH / g. The method for producing a pigment dispersion according to any one of claims 1 to 5, wherein the dispersant having a dye structure is a dispersant having a structure represented by the following general formula (1);
  (D-R ² ) _n -R ¹ -(L ¹ -P) _m             ... (1)
  In general formula (1), R ¹ Represents an (m + n) -valent linking group,
  P represents a monovalent substituent having a repeating unit;
  D represents a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes;
  R ² And L ¹ Each independently represents a single bond or a divalent linking group,
  m represents an integer of 1 to 13,
  when m is 1, P represents a monovalent substituent having two or more repeating units;
  When m is 2 or more, the plurality of Ps may be different from each other, the average value of the number of repeating units constituting the plurality of Ps is 2 or more,
  n represents an integer of 2 to 14,
  when n is 2 or more, the plurality of D may be different from each other;
  m + n represents an integer of 3 to 15.   The method for producing a pigment dispersion according to any one of claims 1 to 5, wherein the dispersant having a dye structure is a multimer containing a repeating unit represented by the following general formula (A);
In general formula (A), X ₁ Represents a linking group formed by polymerization, and L ₁ Represents a single bond or a divalent linking group. DyeI represents a dye structure selected from triarylmethane dyes, xanthene dyes, cyanine dyes and squarylium dyes. A pigment dispersion is produced by the method for producing a pigment dispersion according to any one of claims 1 to 7,
  The manufacturing method of a coloring composition which mixes the obtained pigment dispersion liquid and a curable compound. Furthermore, the manufacturing method of the coloring composition of Claim 8 which mixes a photoinitiator.