JP6147133B2 - Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging device, and image display device - Google Patents

Description

  The present invention relates to a colored composition and a cured film using the same. The present invention also relates to a color filter having a cured film, a method for manufacturing the color filter, a solid-state imaging device having the color filter, and an image display device.

One of the methods for producing color filters used in liquid crystal display devices, solid-state imaging devices, etc. is a pigment dispersion method. As this pigment dispersion method, colored photosensitive materials obtained by dispersing pigments in various photosensitive compositions are used. This is a method for producing a color filter by a photolithography method using a composition. That is, a colored composition is applied on a substrate using a spin coater, a roll coater or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development to obtain a colored pixel. By repeating this operation for a desired hue, a color filter is produced.
The method described above is stable against light and heat because it uses a pigment, and the positional accuracy is sufficiently secured because patterning is performed by a photolithographic method, and it is suitable as a method for manufacturing a color filter for a color display. It has been widely used.

  Patent Document 1 discloses that a colored photosensitive composition containing a dye or a pigment is used for producing a color filter. Patent Document 2 discloses that developability is improved by using a dye multimer containing a xanthene skeleton as a partial structure of a dye part. Patent Document 2 also discloses a combination of a cation moiety and an anion moiety in a dye multimer.

JP 2008-268242 A JP 2012-32754 A

Here, when a colored pattern is formed using a composition containing a site structure derived from a xanthene dye having a cation moiety and a dye multimer having an anion moiety, the line width of the colored pattern is uniform when left for a long time. It turned out that the tendency is inferior.
This invention solves this subject, and it aims at providing the coloring composition which can maintain the uniformity of the line width of a coloring pattern, even if it keeps for a long time.

The present inventor has found that the above problem can be solved by blending a small amount of toluene in a composition containing a dye multimer having a site structure derived from a xanthene dye having a cation moiety and an anion moiety. .
Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <13>.
<1> A coloring composition containing (A) a dye multimer and (B) a solvent,
(A) The dye multimer has a partial structure derived from a xanthene dye having a cation moiety and an anion moiety,
The coloring composition whose toluene concentration in a coloring composition is 0.001-10 ppm.
<2> The colored composition according to <1>, wherein the water content in the colored composition is 0.005 to 3 ppm.
<3> The colored composition according to <1> or <2>, wherein at least one of a sodium ion concentration and a potassium ion concentration in the colored composition is 0.01 to 20 ppm.
<4> The colored composition according to any one of <1> to <3>, wherein the anion moiety is a low nucleophilic anion moiety.
<5> The colored composition according to any one of <1> to <4>, further including a phthalocyanine pigment.
<6> The colored composition according to any one of <1> to <5>, further including a photopolymerization initiator.
<7> The colored composition according to any one of <1> to <6>, further including a curable compound.
<8> The colored composition according to any one of <1> to <7>, which is used for forming a colored layer of a color filter.
<9> A cured film obtained by curing the colored composition according to any one of <1> to <8>.
<10> The step of applying the colored composition according to any one of <1> to <8> on a support to form a colored composition layer, the step of exposing the colored composition layer in a pattern, And a step of developing and removing an unexposed portion to form a colored pattern.
<11> A step of applying the colored composition according to any one of <1> to <8> 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 exposure and development to obtain a resist pattern; and a step of dry etching a colored layer using the resist pattern as an etching mask.
<12> A color filter having the cured film according to <9>, or a color filter manufactured by the method for manufacturing a color filter according to <10> or <11>.
<13> A solid-state imaging device or an image display device having the color filter according to <12>.

  ADVANTAGE OF THE INVENTION According to this invention, even if it left for a long time, it became possible to provide the coloring composition which can maintain the uniformity of the line width of a coloring pattern.

  The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. 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).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, 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 the components excluding the solvent from the total composition of the composition.

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

<Coloring composition>
The colored composition of the present invention (hereinafter also referred to as the composition of the present invention) is a colored composition containing (A) a dye multimer and (B) a solvent, wherein (A) the dye multimer is a cation. It has a partial structure derived from a xanthene dye having a moiety (hereinafter sometimes referred to as “dye structure”) and an anion moiety, and the toluene concentration in the composition of the present invention is 0.001 to 10 ppm, To do.
According to the present invention, the line width of the colored pattern can be kept uniform even when left for a long time. The long-time holding means that the film is left for a long time after the film is formed using the coloring composition and before i-line exposure.

In this invention, the problem which arises by the above-mentioned prolonged holding is solved by mix | blending a small amount of toluene. This mechanism is presumed, but by adding a small amount of toluene, the compatibility between the cation sites in the dye structure and the hydrophobic components in the composition can be improved, and it can be retained for a long time. Even in this case, the line width of the pattern can be kept uniform without causing phase separation. On the other hand, when the toluene concentration is high, toluene aggregates hydrophobic components (eg, curable compounds) in the composition more than necessary. In the present invention, this problem is appropriately solved by setting the toluene concentration within the above range.
In the present invention, for example, even when the holding time is 2 days or longer and 0.3% by mass of tetramethylammonium hydroxide is used as the developer after exposure, the line width of the pattern can be maintained uniformly. .
In the present invention, the toluene concentration in the composition is preferably 0.005 to 10 ppm, preferably 0.01 to 3 ppm, more preferably 0.1 to 3 ppm, and further preferably 0.5 to 2 ppm. .

In the composition of the present invention, the water content in the composition is preferably 0.005 to 3% by mass, more preferably 0.01 to 1% by mass, and 0.05 to 0.15% by mass. Further preferred.
By making the water content 3% by mass or less, it is possible to more effectively suppress separation of the cation moiety and the anion moiety in the dye multimer. In a film formed in a state in which the cation portion and the anion portion are difficult to separate, the photoexcited dye radical is less likely to be trapped by oxygen under a low oxygen concentration, and the dye is more difficult to be decomposed.
In addition, by setting the water content to 0.005% by mass or more, the distance between the cation site and the anion site in the dye multimer is not too close, so that energy transfer and electron transfer during photoexcitation are less likely to occur. The pigment is more difficult to be decomposed. As a result, good light resistance can be maintained even when placed under a low oxygen concentration for a long period of time.
In particular, good light resistance can be maintained even when irradiation is performed for 1 week or more at an illuminance of 10,000 lux under a low oxygen concentration.

In the composition of the present invention, at least one of the sodium ion concentration and the potassium ion concentration in the composition preferably satisfies 0.01 to 20 ppm, more preferably 0.01 to 10 ppm, and more preferably 0.1 to 5 ppm. More preferred is 0.5 to 2 ppm. In particular, it is preferable that both the sodium ion concentration and the potassium ion concentration satisfy the above ranges.
By setting the sodium ion concentration and the potassium ion concentration to 20 ppm or less, the ion exchange reaction between the cation in the dye multimer and at least one of the sodium ion and the potassium ion in the composition is suppressed, the dye structure, and the composition Compatibility with other components (eg, resin, monomer, solvent, etc.) can be further improved, and phase separation in the composition can be effectively suppressed. As a result, even when a film is formed from a composition placed in a low temperature environment (for example, in a refrigerated storage state), foreign matter can be hardly generated. Further, by setting the sodium ion concentration and the potassium ion ion concentration to 0.01 ppm or more, it is possible to effectively suppress the generation of foreign substances due to the compatibility between the dye structure and other components becoming too high.

  From the viewpoint of long-term moisture resistance, the composition of the present invention preferably has a solid content voltage holding ratio of 10 to 80%, more preferably 30 to 60%.

Moreover, in this invention, by setting it as the above structures, a coloring composition with a small rate of change of a viscosity can be obtained after progress for a long period of time. For example, even when the temperature is low (5 ° C. or lower) after 3 months, the rate of change in viscosity can be reduced.
Further, in the present invention, a colored composition having a low incidence of foreign matters when placed in various temperatures (for example, −30 to 150 ° C.) and / or high humidity (for example, relative humidity 80% or more) for a long time. Can be obtained. For example, the occurrence rate of foreign matters can be reduced when placed in a low temperature (5 ° C. or lower) environment for one month or longer, or when placed in an 85 ° C. and 85% RH environment for two weeks or longer.

The composition of the present invention is preferably used for forming a colored layer of a color filter. The coloring composition of the present invention preferably contains a curable compound and a pigment. Examples of the curable compound include a polymerizable compound and an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group), and are appropriately selected depending on the application and production method. Furthermore, the coloring composition of the present invention preferably contains a photopolymerization initiator.
For example, when a colored layer is formed by a photoresist, the colored composition of the present invention preferably contains a dye multimer, a solvent, an alkali-soluble resin as a curable compound, a pigment, and a photopolymerization initiator. Furthermore, components such as a surfactant may be included.
Moreover, when forming a colored layer by dry etching, it is preferable that a pigment | dye multimer, a solvent, the polymeric compound as a sclerosing | hardenable compound, a pigment, and a photoinitiator are included. Furthermore, components such as a surfactant may be included.

<< (A) Dye Multimer >>
Dye multimers include structures such as dimers, trimers and polymers. The dye multimer functions as, for example, a colorant in the coloring composition of the present invention.

The dye multimer has a partial structure derived from a xanthene dye having a cation moiety and an anion moiety. Preferred forms of the dye multimer include the following.
(A1) A dye multimer having a repeating unit having a partial structure derived from a xanthene dye having a cation moiety and having a counter anion moiety.
(A2) A dye multimer comprising a repeating unit having a partial structure derived from a xanthene dye having a cation moiety, wherein the dye structure has an anion moiety.
(A3) A dye multimer comprising a monomer having a partial structure derived from a xanthene dye having a cation moiety and a repeating unit having a counter anion moiety.
(A4) A dye multimer having another cation and anion moiety in the above.
Hereinafter, each embodiment will be described in detail.

<<< Form of (A1) >>>
<<<<< Counter Anion Site >>>>
The counter anion moiety of the dye multimer (A) is preferably non-nucleophilic. Non-nucleophilic means the property of not causing nucleophilic attack on the dye by heating.
The counter anion may be an organic anion or an inorganic anion, and an organic anion is preferred. Examples of the anion include those described in paragraph No. 0075 of JP2007-310315A, the contents of which are incorporated herein.
Preferably, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, tetraarylborate anion, B ⁻ (CN) _n1 (OR ^a ) _4-n1 (R ^a is an alkyl group having 1 to 10 carbon atoms or 6 carbon atoms. Represents an aryl group having 1 to 10, n1 represents 1 to 4) and PF _n2 R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents 1 to 6 Represents an integer), and is more preferably selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion and a tetraarylborate anion, and more preferably a bis (sulfonyl) imide anion. By using such a counter anion, the effect of the present invention tends to be exhibited more effectively.

（式（ＡＮ−１）中、Ｘ¹およびＸ²は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数１〜１０のアルキル基を表す。Ｘ¹およびＸ²は互いに結合して環を形成しても良い。）
Ｘ¹およびＸ²は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数１〜１０のアルキル基を表し、フッ素原子またはフッ素原子を有する炭素数１〜１０のアルキル基が好ましく、炭素数１〜１０のペルフルオロアルキル基であることがより好ましく、炭素数１〜４のペルフルオロアルキル基であることがさらに好ましく、トリフルオロメチル基が特に好ましい。 As a bis (sulfonyl) imide anion, the structure represented by the following general formula (AN-1) is preferable.

(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 are bonded to each other to form a ring. It may be formed.)
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.

（式（ＡＮ−２）中、Ｘ³、Ｘ⁴およびＸ⁵はそれぞれ独立に、フッ素原子または炭素数１〜１０のフッ素原子を有するアルキル基を表す。）
Ｘ³、Ｘ⁴およびＸ⁵は、それぞれ独立に、Ｘ¹およびＸ²と同義であり、好ましい範囲も同義である。 As the tris (sulfonyl) methide anion, a structure represented by the following general formula (AN-2) is preferable.

(In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represents 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.

（式（ＡＮ−５）中、Ａｒ¹、Ａｒ²、Ａｒ³およびＡｒ⁴は、それぞれ独立に、アリール基を表す。） The tetraarylborate anion is preferably a compound represented by the following general formula ((AN-5)).

(In Formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents 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 fluorine. Is more preferable.

The counter anion moiety is also -B (CN) _n1 (OR ^a ) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents 1 to 4 carbon atoms. Preferably represents an integer). R ^a as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
n1 is preferably 1 to 3, and more preferably 1 or 2.

The counter anion site may be —PF ₆ R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6). preferable. R ^P is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a C 1 to 3 perfluoroalkyl group.
n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.

100-1,000 are preferable and, as for the mass per molecule of a counter-anion site | part, 200-500 are more preferable.
The dye multimer may contain only one type of counter anion site, or may contain two or more types.

Specific examples of the counter anion site are shown below, but the present invention is not limited thereto.

<<<<< Dye Structure >>>>
The dye structure in the present invention is a partial structure derived from a xanthene dye having a cation moiety, and a large amount of dye obtained by removing a hydrogen atom from a specific dye that can form a dye structure (hereinafter also referred to as a dye compound). A structure that can be connected to a body connecting part (polymer chain, dendrimer core, etc.). Details of these will be described below.

  The dye structure is not particularly limited as long as it is a structure derived from a xanthene dye having a cation moiety, and various structures including known ones can be applied.

  As a pigment | dye multimer (A), what has the partial structure derived from the xanthene compound represented by the following general formula (J) as a partial structure of a pigment | dye part is contained.

（一般式（Ｊ）中、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³およびＲ⁸⁴は、各々独立に、水素原子または１価の置換基を表し、Ｒ⁸⁵は、各々独立に１価の置換基を表し、ｍは、０〜５の整数を表す。Ｘ^-は、対アニオン部位を表す。）

(In the general formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, and R ⁸⁵ each independently represents a monovalent substituent. , M represents an integer of 0 to 5. X ⁻ represents a counter anion moiety.)

The substituents that can be taken by R ^{81 to} R ⁸⁴ and R ⁸⁵ in formula (J) are the same as the substituents mentioned in the section of substituent group A described later.

In the general 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 to form a 5-, 6-, or 7-membered saturation. A ring or a 5-membered, 6-membered or 7-membered unsaturated ring may be formed. When the formed 5-membered, 6-membered or 7-membered ring is a further substitutable group, it may be substituted with the substituents described for R ^{81 to} R ⁸⁵ above, and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.
R ⁸¹ and R ⁸² in general 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, and have no substituents. 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 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.

  Specific examples of xanthene compounds are shown below, but the present invention is not limited thereto.

  In the dye multimer, hydrogen atoms in the dye structure may be substituted with a substituent selected from the following substituent group A unless departing from the spirit of the present invention.

Substituent group A:
Examples of the substituent that the dye multimer may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group , Aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl Or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group Etc. Details are described below.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms substituted or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3 Yl) or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Oct-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydride Hexyl group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted heterocyclic oxy groups Heterocyclic portion is preferably described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonyla Bruno, butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbocycle having 7 to 30 carbon atoms) D Groups such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl groups (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) A carbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenyl Zo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably 2 carbon atoms). -30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl)

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups. Examples of functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specifically, methylsulfonylaminocarbonyl, Examples include p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

<Structure of dye multimer>
The dye multimer (A) used in the colored composition of the present invention is not particularly defined, but at least one of the repeating units represented by the following general formula (a1-1) and general formula (a1-2). It is preferable that it is a pigment | dye multimer containing one, or a pigment | dye multimer represented by general formula (a1-3). One type of repeating unit represented by formula (a1-1) may be contained in one type of dye multimer, or two or more types of repeating units may be contained. Furthermore, as will be described later, other repeating units may be included.
In this invention, it is preferable that the pigment | dye multimer represented by general formula (a1-1) is included. These will be described sequentially.

（一般式（ａ１−１）中、Ｘ¹は主鎖を形成する基を表し、Ｌ¹は単結合または２価の連結基を表す。ＤｙｅＩはカチオン部位を有する色素構造を表す。）
以下、一般式（ａ１−１）について詳細に説明する。 << Repeating unit represented by formula (a1-1) >>
Formula (a1-1)

(In General Formula (a1-1), X ¹ represents a group forming a main chain, L ¹ represents a single bond or a divalent linking group, and Dye I represents a dye structure having a cation moiety.)
Hereinafter, the general formula (a1-1) will be described in detail.

In General Formula (a1-1), X ¹ represents a group that forms a main chain. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but linking groups represented by the following (XX-1) to (X-24) are particularly preferred, (XX -1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, and (XX-24) More preferably selected from vinyl-based connecting chains, (meth) acrylic connecting chains represented by (XX-1) and (XX-2) and styrene-based connecting chains 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 (a1-1), L ¹ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, the divalent linking group includes a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene). Group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene 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 linkage formed by linking two or more thereof. Represents a group. L ¹ is more preferably a single bond or an alkylene group, and more preferably a single bond or — (CH ₂ ) n — (n is an integer of 1 to 5). Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
The divalent linking group represented by L ¹ may be a group capable of ionic bonding or coordination bonding with DyeI. In this case, either an anionic group or a cationic group may be used.
Examples of the anionic group include —COO ⁻ , —PO ₃ H ⁻ , —SO ₃ ⁻ , —SO ₃ NH ⁻ , —SO ₃ N ^— CO—, and the like, —COO ⁻ , —PO ₃ H ⁻ , — SO ₃ ^- is preferred.
Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, phosphonium and the like), and ammonium cations are particularly preferable.
When L ¹ has a group capable of ionic bonding or coordination bond with Dye I, L ¹ is an anion moiety (—COO ⁻ , —SO ₃ ⁻ , —O ⁻ etc.) or a cation moiety (the above-mentioned) that Dye I has. An onium cation, a metal cation, etc.).

  In the general formula (a1-1), DyeI represents a dye structure derived from the above-described dye compound.

The dye multimer having the repeating unit represented by the general formula (a1-1) is (1) a method of synthesizing a monomer having a dye residue by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy group. It can be synthesized by a method of reacting a polymer having a highly reactive functional group such as a dye with a functional group capable of reacting with the highly reactive group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.).
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.
Among them, the dye multimer having the repeating unit represented by the general formula (a1-1) 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.

  Specific examples of the repeating unit represented by general formula (a1-1) are shown below, but the present invention is not limited thereto.

（一般式（ａ１−２）中、Ｌ³は単結合または２価の連結基を表す。ＤｙｅＩＩＩは、カチオン部位を有する色素構造を表す。ｍは０または１を表す。） << Repeating unit represented by formula (a1-2) >>
Next, the dye multimer represented by the general formula (a1-2) will be described in detail.
Formula (a1-2)

(In general formula (a1-2), L ³ represents a single bond or a divalent linking group. DyeIII represents a dye structure having a cation moiety. M represents 0 or 1.)

In general formula (a1-2), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ³ include a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene group). Etc.), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S- , -NR- (R is each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,.), - C (= O) -, - SO -, - SO 2 -, and these Preferable examples include a linking group formed by linking two or more.
m represents 0 or 1, but is preferably 1.

Setting forth specific examples to be preferably used as the divalent linking group represented by L ³ in the general formula (a1-2) are shown below, but the invention is not limited thereto as L ³ of the present invention . In addition, the site | part shown by * represents the connection site | part with DyeIII etc.

  The dye multimer having the repeating unit represented by the general formula (a1-2) is synthesized by sequential polymerization. Sequential polymerization means polyaddition (for example, reaction of diisocyanate compound and diol, reaction of diepoxy compound and dicarboxylic acid, reaction of tetracarboxylic dianhydride and diol, etc.) and polycondensation (for example, dicarboxylic acid). And a diol, a reaction of a dicarboxylic acid and a diamine, and the like. Among these, synthesis by polyaddition reaction 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 sequential polymerization.

  Specific examples of the repeating unit represented by general formula (a1-2) are shown below, but the present invention is not limited thereto.

<< Dye Multimer Represented by General Formula (a1-3) >>
Next, the dye multimer represented by the general formula (a1-3) will be described in detail.

（一般式（ａ１−３）中、Ｌ⁴はｎ価の連結基を表す。ｎは２〜２０の整数を表す。ＤｙｅＩＶは、カチオン部位を有する色素構造を表す。） Formula (a1-3)

(In General Formula (a1-3), L ⁴ represents an n-valent linking group. N represents an integer of 2 to 20. DyeIV represents a dye structure having a cation moiety.)

In general formula (a1-3), n is preferably 3 to 15, particularly preferably 3 to 6.
In the general formula (a1-3), when n is 2, the divalent linking group represented by L ⁴ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group or an ethylene group). , Trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH -, -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), -C (= O)-, -SO-. , —SO ₂ —, and a linking group formed by linking two or more of these are preferable.

  The n-valent linking group where n is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.) And a linking group formed by substituting the divalent linking group with a heterocycle linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.

Specific examples of L ⁴ in general formula (a1-3) are shown below, but the present invention is not limited thereto. In addition, the site | part shown by * represents the connection site | part with DyeIV.

  Specific examples of DyeIV in general formula (a1-3) are shown below, but the present invention is not limited thereto.

  Of the dye multimer having at least one repeating unit represented by general formula (a1-1) and general formula (a1-2), and the dye multimer represented by general formula (a1-3) And a dye multimer having a repeating unit represented by the general formula (a1-1), a dye multimer having a repeating unit represented by the general formula (a1-2), and a general formula (a1-3) In the dye multimer, since the partial structure derived from the dye is covalently linked in the molecular structure, the coloring composition containing the dye multimer is excellent in heat resistance. For this reason, when a coloring composition is applied to pattern formation which has a high temperature process, since it is effective in the color transfer suppression to other adjacent coloring patterns, it is preferable. In particular, the compound represented by the general formula (a1-1) is preferable because the molecular weight of the dye multimer can be easily controlled.

<< Other functional groups and repeating units >>
The dye multimer may have another functional group in the dye structure portion of the dye multimer described above. Examples of other functional groups include polymerizable groups, acid groups, and alkali-soluble groups.
The dye multimer may contain other repeating units in addition to the repeating unit containing the dye structure described above. Other repeating units may have a functional group.
Moreover, as another repeating unit, the repeating unit containing at least 1 sort (s) of a polymeric group, an acid group, and an alkali-soluble group is illustrated.
That is, the dye multimer may have other repeating units in addition to the repeating units represented by the general formulas (a1-1) to (a1-3). One type of other repeating unit may be included in one dye multimer, or two or more types may be included.
The dye multimer may have other functional groups in the dye multimer represented by the general formulas (a1-1) to (a1-3). Details of these will be described below.

<<< Polymerizable group of dye multimer (A) >>>
The dye multimer preferably contains a polymerizable group. One type of polymerizable group may be included, or two or more types may be included.
As for the polymerizable group, the dye structure may contain a polymerizable group, or may contain other parts. In the present invention, the dye structure preferably includes a polymerizable group. By adopting such a configuration, the heat resistance tends to be improved.
Moreover, in this invention, the aspect in which other parts other than a pigment | dye structure contain a polymeric group is also preferable.
As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), or a methylol group. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate-derived (meth) More preferred is an acryloyl group.
The polymerizable group is preferably contained as a repeating unit having a polymerizable group in the dye multimer, and more preferably as a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye multimer is an embodiment in which the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having a polymerizable group. The repeating unit containing a dye monomer and ethylene It is more preferable to contain a repeating unit having a polymerizable unsaturated bond.

  As a method for introducing a polymerizable group, (1) a method in which a dye multimer is modified and introduced with a polymerizable group-containing compound, and (2) a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced. Etc. Details will be described below.

(1) A method of introducing a dye multimer after modifying it with a polymerizable group-containing compound:
As a method for introducing the dye multimer by modifying with a polymerizable group-containing compound, a known method can be used without any particular limitation. For example, (a) a method of reacting a carboxylic acid contained in a dye multimer with an unsaturated bond-containing epoxy compound, and (b) a method of reacting a hydroxyl group or amino group of the dye multimer with an unsaturated bond-containing isocyanate compound. (C) A method of reacting an epoxy compound contained in the dye multimer with an unsaturated bond-containing carboxylic acid compound is preferable from the viewpoint of production.

  (A) As the unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid of the dye multimer with the unsaturated bond-containing epoxy compound, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3,4-epoxycyclohexyl Examples thereof include methyl acrylate and 3,4-epoxy-cyclohexylmethyl methacrylate, and glycidyl methacrylate and 3,4-epoxy-cyclohexylmethyl methacrylate are particularly preferable because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.

  (B) As the unsaturated bond-containing isocyanate compound in the method of reacting the hydroxyl group or amino group of the dye multimer with the unsaturated bond-containing isocyanate compound, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl atacrylate, Examples include 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and 2-isocyanatoethyl methacrylate is preferable because of its excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.

  (C) The unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the dye multimer with the unsaturated bond-containing carboxylic acid compound is particularly a carboxylic acid compound having a known (meth) acryloyloxy group Although it can be used without limitation, methacrylic acid and acrylic acid are preferable, and methacrylic acid is particularly preferable because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.

(2) A method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced:
(2) As a method for copolymerizing and introducing a dye monomer and a polymerizable group-containing compound, known methods can be used without any particular limitation. (D) A radically polymerizable dye monomer and a radical can be used. A method of copolymerizing a polymerizable group-containing compound that can be polymerized, and a method (e) a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition are preferred.

  (D) As a radically polymerizable polymerizable group-containing compound in a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable polymerizable group-containing compound, an allyl group-containing compound (for example, (meth)) Allyl acrylate, etc.), epoxy group-containing compounds (eg, glycidyl (meth) acrylate, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, etc.), oxetane group-containing compounds (eg, 3-methyl-3-oxetanylmethyl (meth) ) Acrylate etc.) and methylol group-containing compounds (for example, N- (hydroxymethyl) acrylamide etc.), and epoxy compounds and oxetane compounds are particularly preferred. Known conditions can be used as the reaction conditions.

  (E) As a polymerizable group-containing compound capable of polyaddition in a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition, an unsaturated bond-containing diol compound (for example, 2, 3-dihydroxypropyl (meth) acrylate). Known conditions can be used as the reaction conditions.

  As a method for introducing a polymerizable group, a method of reacting a carboxylic acid possessed by a dye multimer, a carboxylic acid possessed by a dye multimer, and an unsaturated bond-containing epoxy compound is particularly preferred.

The polymerizable group amount of the dye multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, with respect to 1 g of the dye multimer (A), and 0.3 -1.0 mmol is particularly preferred.
Moreover, the ratio of the repeating unit containing the repeating unit in which the dye multimer has a polymerizable group is preferably, for example, 5 to 50 mol, and more preferably 10 to 20 mol with respect to 100 mol of all repeating units.

  As a method for introducing a polymerizable group, a method of reacting a carboxylic acid possessed by a dye multimer, a carboxylic acid possessed by a dye multimer, and an unsaturated bond-containing epoxy compound is particularly preferred.

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

  Among the specific examples described above, from the viewpoint of substrate adhesion and surface roughness, a dye monomer having an ethylenically unsaturated bond is preferable, among which a methacryloyl group, an acryloyl group, a styryl group, or a vinyloxy group is preferable, and a methacryloyl group. An acryloyl group is more preferable, and a methacryloyl group is more preferable.

<<< Acid group and alkali-soluble group of dye multimer (A) >>>
Examples of the acid group that the dye multimer may have include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Examples of the alkali-soluble group include phenolic hydroxyl groups and carboxylic acids.
In the present invention, it is preferable that the acid group and / or alkali-soluble group is contained in the dye multimer as a repeating unit having an acid group and / or alkali-soluble group.
The acid value of the repeating unit having an acid group is preferably 15 mgKOH / g to 110 mgKOH / g, more preferably 20 mgKOH / g to 90 mgKOH / g, and 30 mgKOH / g to 60 mgKOH / g. Further preferred.
The acid value of the dye multimer can be calculated from, for example, the average content of acid groups in the dye multimer. Moreover, the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises a pigment | dye multimer.

  As a method for introducing an alkali-soluble group into a dye multimer, a method in which an alkali-soluble group is introduced into a dye monomer in advance, and a monomer other than a dye monomer having an alkali-soluble group ((meth) acrylic acid, acrylic Modified product of caprolactone of acid, modified product of succinic anhydride of 2-hydroxyethyl (meth) acrylate, modified product of phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-hydroxyethyl (meth) acrylate 2-cyclohexanedicarboxylic acid anhydride modified product, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomer such as acid phosphooxyethyl methacrylate, vinyl phosphonic acid, vinyl sulfonic acid, Such as 2-acrylamido-2-methylsulfonic acid A method of copolymerizing a phosphate-containing monomer) may be mentioned, more preferably to use both methods.

The amount of the alkali-soluble group that the dye multimer has is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and more preferably 0.5 mmol to 1. Particularly preferred is 0 mmol.
Further, when the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is 100 repeating units containing a dye monomer. For example, 5-70 mol is preferable with respect to mol, and 10-50 mol is more preferable.

Other functional groups possessed by the dye multimer include lactones, acid anhydrides, amides, —COCH ₂ CO—, development promoting groups such as cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups And an affinity adjusting group such as a hydroxyl group, a maleimide group, and an amino group, and the like, which can be appropriately introduced.
Examples of the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.

  Although the specific example of the repeating unit which has another functional group which a pigment | dye multimer has is shown, this invention is not limited to this.

<<< Form of (A2) >>>
The form (A2) of the dye multimer is a dye multimer having a repeating unit having a dye structure and having an anion moiety in the dye structure.
For example, the dye multimer preferably includes a repeating unit represented by the general formula (a2).

（一般式（ａ２）中、Ｘ¹は主鎖を形成する基を表し、Ｌ¹は単結合または２価の連結基を表す。ＤｙｅＩＡはカチオン部位およびアニオン部位を有する色素構造を表す。）
一般式（ａ２）中、Ｘ¹およびＬ¹は上述した一般式（ａ１−１）と同義であり、好ましい範囲も同様である。
一般式（ａ２）中、ＤｙｅＩＡは、上述した一般式（ａ１−１）中のＤｙｅＩが、さらにアニオン部位を有するものである。アニオン部位としては、−ＳＯ^3-、−ＣＯ₂ ^2-等が挙げられる。 Formula (a2)

(In the general formula (a2), X ¹ represents a group forming a main chain, L ¹ represents a single bond or a divalent linking group. DyeIA represents a dye structure having a cation moiety and an anion moiety.)
In General Formula (a2), X ¹ and L ¹ have the same meanings as those of General Formula (a1-1) described above, and the preferred ranges are also the same.
In General Formula (a2), DyeIA is one in which DyeI in General Formula (a1-1) described above further has an anion moiety. Examples of the anion moiety include —SO ³⁻ , —CO ₂ ^{2− and the} like.

  As specific examples of the form (A2) of the dye multimer, A-1, A-3 to A-6 described in paragraph 0069 of JP2012-032754A can be referred to, and the contents thereof are described in this specification. Incorporated.

（一般式（ａ３）中、Ｘ¹は主鎖を形成する基を表し、Ｌ²は単結合または２価の連結基を表し、Ｚは対アニオン部位を有する構造を表す。） <<< Form of (A3) >>>
The form (A3) of the dye multimer is a dye multimer comprising a monomer having a dye structure and a repeating unit having a counter anion site.
The monomer which has a pigment structure is synonymous with the monomer containing the partial structure derived from the xanthene compound represented by the general formula (J) mentioned above.
The repeating unit having a counter anion moiety preferably includes a repeating unit represented by the following general formula (a3).
General formula (a3)

(In general formula (a3), X ¹ represents a group forming a main chain, L ² represents a single bond or a divalent linking group, and Z represents a structure having a counter anion site.)

In general formula (a3), X ¹ has the same meaning as in general formula (a1-1) described above, and the preferred range is also the same.
In the general formula (a3), when L ² represents a divalent linking group, an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10) or an arylene group having 6 to 20 carbon atoms (preferably 6 to 10). A heterocyclic group having 4 to 20 carbon atoms (preferably 5 to 10), an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10), and an arylsulfonyl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. , An alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), an arylcarbonyl group having 6 to 20 carbon atoms (preferably 6 to 11), and an alkyl having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). Amino group, C6-C20 (preferably 6-10) arylamino group, C1-C20 (preferably 1-10) alkylcarbonyloxy group, C6-C20 (preferably 6-11) The aryl Such as Ruboniruokishi group, and the like. These divalent linking groups are preferably substituted with an electron-withdrawing group. Examples of the electron-withdrawing group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, cyano group, Examples thereof include a halogenated alkyl group (for example, a trifluoromethyl group) and a halogenated aryl group.
L ² is substituted with a fluorine atom having 1 to 10 carbon atoms when Z in the general formula (1) described later is a low nucleophilic anion structure represented by the general formula (2-1). An alkylene group (fluorinated alkylene group) is preferred.

（一般式（２−３）中、＊は、一般式（ａ３）中のＬ²との結合部位を表し、Ｒは、それぞれシアノ基、またはフッ素化アルキル基を表し、シアノ基が好ましい。） In general formula (a3), Z is a group represented by general formula (2-1), a fluorinated alkylsulfonimide group or a fluorinated alkylsulfonemethide group, or a group represented by general formula (2-3). Is preferably represented.
General formula (2-1)
* -Y ¹ -A ¹
(In the general formula (2-1), * represents a binding site with L ² in the general formula (a3), Y ¹ represents a fluorinated alkylene group, A ¹ is SO ₃ ^- represents a.)
General formula (2-3)

(In General Formula (2-3), * represents a binding site with L ² in General Formula (a3), R represents a cyano group or a fluorinated alkyl group, and a cyano group is preferred.)

Hereinafter, although the specific example of the repeating unit represented by general formula (a3) used by this invention is shown, this invention is not limited to this. In addition, although the specific example has shown the state which the anion site | part has not dissociated, it cannot be overemphasized that the state which the anion site | part has dissociated is also in the scope of the present invention.

<<< Form of (A4) >>>
The form (A4) of the dye multimer is a dye multimer having other cation and anion sites. For example, a monomer having a dye structure and a repeating unit having a cation moiety, and the monomer having a dye structure is a dye multimer containing a corresponding anion moiety.
As the repeating unit having a cation moiety, the description in paragraphs 0018 to 0061 of JP2011-242752A can be referred to, and the contents thereof are incorporated herein.
Examples of the monomer having a dye structure containing a corresponding anion moiety include C.I. I. Acid Red 289 is exemplified.
As a specific example of the dye multimer (A4), the description in paragraph 0165 of JP2011-242752A can be referred to, and the contents thereof are incorporated in the present specification.

The dye multimer preferably has a maximum absorption wavelength of 420 to 700 nm, and more preferably 450 to 650 nm.
The acid value of the dye multimer is preferably 5 to 100 mgKOH / g, and more preferably 15 to 60 mgKOH / g.
In this invention, when the repeating unit containing the structure derived from a pigment | dye makes a total repeating unit 100 mol%, it is preferable that it is 10-100 mol% in a pigment | dye multimer, and it is 50-100 mol%. More preferably, it is 60-100 mol% especially preferable.
The weight average molecular weight of the dye multimer is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and particularly preferably 4,000 to 10,000.
The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).
Further, the ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dye multimer is preferably 1.0 to 3.0, and preferably 1.6 to 3.0. More preferably, it is 2.5, and it is especially preferable that it is 1.6-2.0.

  The glass transition temperature (Tg) of the dye multimer is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher.

  Further, the extinction coefficient per unit weight of the dye multimer (hereinafter referred to as ε ′; ε ′ = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, and preferably 60 or more. Is more preferable, and 100 or more is more preferable. By being in this range, when a color filter is produced by applying the colored composition of the present invention, a color filter with good color reproducibility can be produced.

  The molar extinction coefficient of the dye multimer is preferably as high as possible from the viewpoint of coloring power.

  The reduced viscosity of the dye multimer is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and 6.0 to 7.0 from the viewpoint of color transfer. More preferably. The reduced viscosity can be measured using, for example, an Ubbelohde viscometer.

The dye multimer is preferably a compound that dissolves in the following solvent.
Examples of the solvent include esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), and aromatic hydrocarbons (eg, toluene, xylene, etc.). On the other hand, it is preferable to dissolve 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and further preferably 10% by mass to 30% by mass. By being in this region, when the colored composition of the present invention is applied to the production of a color filter or the like, it becomes possible to reduce a decrease in density due to a suitable coated surface shape or elution after application of other colors. .

  In the colored composition of the present invention, the dye multimer may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to content mentioned later.

The content of the dye multimer (A) in the colored composition of the present invention is preferably set in consideration of the content ratio with the (B) pigment described later.
The mass ratio of the dye multimer to the pigment (dye multimer (A) / pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.

The coloring composition of this invention may contain well-known dyes other than the pigment | dye multimer mentioned above.
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. Specification, 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, JP 2010-250291 A, JP 2011-95732 A, JP 2012-13945 A, JP 2012-46708 A, JP 2012-46712 A, JP 2012-181502 A, JP JP2012-208494A, JP2013-28764A, JP2013-29A. Can be referred to 60 JP, the contents of which are incorporated herein. The chemical structure includes pyrazole azo, pyromethene, anilinoazo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc. Dyes can be used.

<< (B) Solvent >>
The coloring composition of the present invention contains a solvent.
The solvent 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 UV absorbers, alkali-soluble resins and dispersants, etc. Is preferably selected in consideration of

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, 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 (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 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. As 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 monomethyl ether acetate, Examples of propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, cyclopentanone, and aromatic hydrocarbons For example, toluene, xylene and the like are preferable.
Among these, a solvent having a molecular weight in the range of 80 to 135 or a boiling point in the range of 120 to 160 ° C. is preferable from the viewpoint of drying after coating. Applicable to these are n-butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and cyclopentanone.

  In addition to the above viewpoint, these organic solvents contain 10% or more of a solvent excellent in solubility of xanthene dyes, such as cyclohexanone, cyclopentanone, and propylene glycol monomethyl ether, to improve the holding stability. It can be improved further. As a specific example, containing propylene glycol monomethyl ether acetate as a main solvent and containing at least 10% of one or more solvents selected from cyclohexanone, cyclopentanone, and propylene glycol monomethyl ether Both improvements can be achieved.

The content of the solvent in the colored composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 50% by mass is particularly preferred.
The composition of the present invention 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.

<Curable compound>
The colored composition of the present invention preferably contains a curable compound.
As the curable compound, a known polymerizable compound that can be cross-linked by a radical, acid, or heat can be used. For example, a polymerizable compound containing an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane), methylol, or the like can be used. 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 is preferable, a polyfunctional polymerizable compound having 4 or more functions is more preferable, 5 functions or more is more preferable, and 6 functions or more is particularly preferable.
In particular, it is a polyfunctional monomer (preferably tetrafunctional or higher, more preferably hexafunctional or higher), and an alkylene oxide-modified one is preferable.

  Such a compound group is widely known in the industrial field, and these can be used without 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.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in JP-A-2009-288705, paragraphs 0095 to 0108 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. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as nurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A Urethane (meth) acrylates as described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Other preferable polymerizable compounds include a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated group. It is also possible to use a compound having two or more functions, a cardo resin.

  Moreover, 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, paragraph numbers [0254] to [0257] of JP-A-2008-292970 are disclosed. Also suitable are the compounds described in.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH ₂ or —OC. A group represented by (═O) C (CH ₃ ) ═CH ₂ is represented.
Specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) include the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.

  Moreover, the compound which (meth) acrylate-ized after adding ethylene oxide and propylene oxide to the said polyfunctional alcohol described with the specific example as general formula (1) and (2) in Unexamined-Japanese-Patent No. 10-62986 is also, It can be used as a polymerizable compound.

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

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is 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 Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polyfunctional monomer 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, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

  In the general formula (Z-1), all six Rs 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 a number 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. )

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

  The specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

In the general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —. Y represents each independently an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (Z-4), the sum total of acryloyl group and 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. is there. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the 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 the 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 the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (ii), 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 above general formula (Z-4) or general formula (Z-5) is a conventionally known process, in which ethylene oxide or propylene oxide is ring-opened to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition 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 (i) or (ii).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives 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)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

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

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as 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 curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  Examples of the cyclic ether (epoxy, oxetane) include those having an epoxy group such as JER-827, JER-828, JER-834, JER-1001, JER-1002, and JER-1003 as bisphenol A type epoxy resins. Bisphenol F As a type epoxy resin, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON830 EPICLON 835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and phenol novolac type epoxy resins such as JER-152, JER-154, JER- 157S70, JER-157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. As cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) , EO CN-1020 (manufactured by Nippon Kayaku Co., Ltd.), as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation) Celoxide 2021P, Celoxide 2081 Celoxide 2083, Celoxide 2085, EHPE-3150 (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol), EPOLEEAD PB 3600, PB 4700 (Above, manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-401 S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER -1031S (made by Japan Epoxy Resin Co., Ltd.) and the like. Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

About these polymeric compounds, the details of usage methods, such as the structure, single use or combined use, and addition amount, can be arbitrarily set according to the final performance design of a coloring composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the cured film formed from the colored composition, those having three or more functional groups are preferable, and further, different numbers of functional groups / different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, A method of adjusting both sensitivity and strength by using a combination of vinyl ether compounds) is also effective. Furthermore, it is preferable to use a tri- or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the colored composition can be adjusted and an excellent pattern forming ability can be obtained.
In addition, the compatibility and dispersibility with other components (for example, photopolymerization initiators, dispersions, alkali-soluble resins, etc.) contained in the colored composition are also selected and used as a polymerizable compound. This is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

The content of the curable compound in the composition of the present invention is preferably 0.1 to 90% by mass, more preferably 1.0 to 60% by mass with respect to the total solid content in the composition, and 2.0 to 40% by mass is particularly preferred.
The composition of the present invention may contain only one type of curable compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Pigment>
The colored composition of the present invention preferably further contains (C) a pigment.
As the pigment used in the present invention, 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. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And black pigments such as composite oxides of the above metals, carbon black and titanium black.

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 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
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;
Etc.

  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 , Etc. 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. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm. When the ratio is 100: 51 or more, the main wavelength tends to be closer to the short wavelength, and the color resolution may not be improved. In particular, the mass ratio is optimally 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 required 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. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof 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 and the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

  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.

  The coloring composition of the present invention preferably contains a pigment other than black, and is suitable for a blue pigment.

When used for a color filter, the primary particle size 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 size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.

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 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 particularly preferred.
In particular, a phthalocyanine pigment is preferable as the pigment.

When a phthalocyanine pigment is used as the pigment, the mass ratio of the phthalocyanine pigment to the above-described dye multimer is preferably phthalocyanine pigment: dye multimer = 100: 10 to 100: 100, and more preferably 100: 20 to 100: 80.
As for content of a pigment, 10-70 mass% is preferable with respect to all the components except the solvent contained in a coloring composition, More preferably, it is 20-60 mass%, More preferably, it is 25-50 mass%. It is.
The content in the case of using a phthalocyanine pigment as the pigment is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably based on all components excluding the solvent contained in the coloring composition. Is 25-50 mass%.
The composition 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.

<Photopolymerization initiator>
The colored composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of further improving sensitivity.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the 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, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like, and oxime compounds are preferred.

  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.

トリアリールイミダゾール化合物、ベンゾイミダゾール化合物としては、以下の化合物が例示される。

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, onium compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.
Specifically, examples of the trihalomethyltriazine compound include the following compounds. Note that Ph is a phenyl group.

Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.

A commercially available product can be used as the trihalomethyltriazine compound, for example, TAZ-107 (manufactured by Midori Chemical Co., Ltd.) can also be used.
In particular, when the colored composition of the present invention is used for the production of a color filter included in a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it is developed without any problems. From such a viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. In view of these points, it is particularly preferable to use an oxime compound as the photopolymerization initiator (D) in order to form a fine pattern such as a solid-state imaging device.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in paragraph No. 0075 of JP2013-077009A, and the like.

  Moreover, an acridine derivative is illustrated as photoinitiators other than the above. Specific examples include the compounds described in paragraph No. 0076 of JP2013-077009A, and the contents thereof are incorporated in the present specification.

  Examples of the ketone compound include compounds described in paragraph No. 0077 of JP2013-077009A, and the contents thereof are incorporated in the present specification.

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-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. 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 compound 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.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  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, and ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are 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, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

Particularly preferred are oxime compounds having a specific substituent as disclosed in JP-A-2007-269979 and oxime compounds having a thioaryl group as described in JP-A-2009-191061.
Specifically, the oxime compound that is a photopolymerization initiator is preferably a compound represented by the following general 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.

  As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable. Specifically, paragraph 0025 of JP-A-2009-191061 can be referred to, and the contents thereof are incorporated herein.

  As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and specifically, paragraph 0026 of JP-A-2009-191061 can be referred to, the contents of which are incorporated herein.

  As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable, and specifically, paragraph 0033 of JP-A-2009-191061 can be referred to, and the contents thereof are incorporated herein.

  As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable. Specifically, paragraph 0034 of JP-A-2009-191061 can be referred to, and the contents thereof are incorporated herein.

  Specifically, an aryloxycarbonyl group having 6 to 30 carbon atoms is preferred as the aryloxycarbonyl group, and paragraph 0035 of JP-A-2009-191061 can be referred to, the contents of which are incorporated herein.

As the heterocyclic group, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable.
Specifically, paragraph 0037 of JP 2009-191061 A can be referred to, and the contents thereof are incorporated in the present specification.

  Specifically, the alkylthiocarbonyl group is preferably an alkylthiocarbonyl group having 1 to 20 carbon atoms, and can be referred to paragraph 0038 of JP-A-2009-191061, the contents of which are incorporated herein.

  Specifically, an arylthiocarbonyl group having 6 to 30 carbon atoms is preferable as the arylthiocarbonyl group, and paragraph 0039 of JP-A-2009-191061 can be referred to, the contents of which are incorporated herein.

  In General Formula (OX-1), the monovalent substituent represented by B represents 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. Moreover, the substituent mentioned above may be further substituted by another substituent.

  Among them, paragraph 0044 of JP2009-191061 can be particularly preferably referred to, and the contents thereof are incorporated in the present specification.

In the formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A in the formula (OX-1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Group) substituted alkylene group, alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl) Group, a phenanthryl group, and a styryl group) are preferable.

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (OX-1), a preferable structure of “SAr” formed by Ar in the formula (OX-1) and S adjacent thereto is described in paragraph 0049 of JP-A-2009-191061. Which is incorporated herein by reference.

  For the oxime compound, the description in paragraphs 0050 to 0106 of JP-A-2009-191061 can be referred to, and the contents thereof are incorporated herein.

  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 high absorbance at 365 nm and 455 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, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

When the colored composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably based on the total solid content of the colored composition. It is 0.5-30 mass%, More preferably, it is 1-20 mass%. Within this range, better sensitivity and pattern formability can be obtained.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Pigment dispersant>
When the coloring composition of the present invention has a pigment, a pigment dispersant can be used in combination as desired.
Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include a polyester-based dispersant, specifically, JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, and JP-A-10-339949 Copolymers of macromonomer and nitrogen atom monomer described in JP-A-2004-37986, International Publication Pamphlet WO2010 / 110491, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A Grafts having partial skeletons and heterocyclic rings of organic dyes described in JP-A-2008-81732 Polymer, and a copolymer of a macromonomer and acid group-containing monomers described in JP 2010-106268 Publication. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 has the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion. From the viewpoint of

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-272 And polyester-based macromonomers described in Japanese Patent No. 009. Among these, a polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, Furthermore, a polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is particularly preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The pigment dispersant that can be used in the present invention is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate) manufactured by BYK Chemie. ), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), “EFKA 4047, 4050 to 4010 to 4165 (polyurethane system), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), manufactured by EFKA, 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) manufactured by Kyoeisha Chemical Co., Ltd. ) ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid) ”, # 7004 (poly) Ether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate) ", MS, C, SN-B (aromatic sulfonic acid formalin) manufactured by Kao Corporation Polycondensate) ”,“ homogenol L-18 (polymeric polycarbohydrate) Acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 86 (stearylamine acetate) "," Solsperse 5000 (phthalocyanine derivative) "manufactured by Nippon Lubrizol Co., Ltd., 22000 ( Azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 manufactured by Nikko Chemicals ” (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawano Fine Chemical Co., Ltd. Hinoact T-8000E, etc., Shin-Etsu Chemical Co., Ltd., organosiloxane polymer P341, Yusho Co., Ltd. “W001: Cationic surfactant”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, Nonionic surfactants such as polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47 manufactured by Morishita Sangyo Co., Ltd.” , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by San Nopco" Disperse Aid 6, Disperse Aid " , Disperse Aid 15, Disperse Aid 9100, etc., manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant may be used in combination with an alkali-soluble resin together with the terminal-modified polymer, graft polymer, or block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples thereof include acidic cellulose derivatives, and (meth) acrylic acid copolymers are particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.

In the coloring composition, when the pigment dispersant is contained, the total content of the pigment dispersant is preferably 1 part by mass to 80 parts by mass with respect to 100 parts by mass of the pigment, and 5 parts by mass to 70 parts by mass. Part is more preferable, and it is further more preferable that it is 20 mass parts-40 mass parts.
The composition of the present invention may contain only one type of pigment dispersant, or two or more types of pigment dispersants. When two or more types are included, the total amount is preferably within the above range.

Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts by mass in terms of mass with respect to 100 parts by mass of the pigment, and 10 to 80 parts by mass. More preferred is the range of parts.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1 mass part-30 mass parts in conversion of mass as a usage-amount of a pigment derivative with respect to 100 mass parts of pigments, 3 mass parts-20 mass parts. More preferably, it is in the range, and particularly preferably in the range of 5 to 15 parts by mass.

  In the coloring composition, from the viewpoint of curing sensitivity and color density, the total content of the coloring agent and the dispersing agent component is 50% by mass or more and 90% by mass or less with respect to the total solid content constituting the coloring composition. Is more preferable, 55 mass% or more and 85 mass% or less is more preferable, and 60 mass% or more and 80 mass% or less is further more preferable.

<Alkali-soluble resin>
The coloring composition of the present invention preferably further contains an alkali-soluble resin.
The molecular weight of the alkali-soluble resin is not particularly defined, but it is preferable that Mw is 5000 to 100,000. Moreover, it is preferable that Mn is 1000-20,000.
The weight average molecular weight of the compound used in the present invention is defined as a polystyrene converted value by GPC measurement. The weight average molecular weight and number average molecular weight are, for example, HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column, and eluent. It can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution.

  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 the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  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.

  The alkali-soluble resin may include a polymer (a) obtained by polymerizing a monomer component which essentially includes a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”). preferable.

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.

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 (1) showing the ether dimer, 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. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. 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, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (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-prope , 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-butyl) Cyclohexyl) -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.

Moreover, in order to improve the crosslinking efficiency of the coloring composition in this invention, it is preferable to use the alkali-soluble resin which has a polymeric group. 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 polymer containing a polymerizable group include: Diamond NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., manufactured by), Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. 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.

  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. Are 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. Is 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 acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g.
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 coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1% by mass to 15% by mass, more preferably 2% by mass with respect to the total solid content of the coloring composition. It is -12 mass%, Most preferably, it is 3 mass%-10 mass%.
The composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types, but preferably contains two or more types, and at least one type has a polymerizable group. It is more preferable. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
In addition to the above-mentioned components, the colored composition of the present invention is a range that does not impair the effects of the present invention, and further includes a surfactant, a crosslinking agent, a polymerization inhibitor, an organic carboxylic acid, an organic carboxylic acid anhydride, and the like. Other components may be included.

<< 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.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by 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 Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  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 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol Japan Co., Ltd.), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), 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 Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
When the coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass with respect to the total mass of the coloring composition, more preferably It is 0.05 mass%-1.0 mass%.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<< Crosslinking agent >>
It is also possible to further increase the hardness of the cured film obtained by curing the colored composition by using a crosslinking agent in the colored composition of the present invention.
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. Of these, polyfunctional epoxy resins are preferred.
The details of paragraphs 0134 to 0147 of JP-A No. 2004-295116 can be referred to for details such as specific examples of the crosslinking agent.
When the coloring composition of the present invention contains a crosslinking agent, the blending amount 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 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.

<< 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-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the coloring composition of the present invention contains a polymerization inhibitor, the addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the mass of the entire composition.
The 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.

<< Organic carboxylic acid, organic carboxylic 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.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

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 composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the residual undissolved coloring composition while maintaining high pattern adhesion. .

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.
The composition of the present invention may contain only one type of the above components, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<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 prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm, more preferably about 0.05 μm to 0.5 μm. Can be provided.
In addition, when a pigment is blended in the composition of the present invention, it is preferable to use a washed pigment. By using the washed pigment, foreign matters in the composition can be further reduced. Paragraphs 0011 to 0099 of JP 2010-83997 A can be referred to for the method for washing the pigment, the contents of which are incorporated herein.

  The colored composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film having excellent heat resistance and color characteristics, it is suitably used for forming a colored pattern (colored layer) of a color filter. . The colored composition of the present invention is preferably used for forming a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS, etc.) or an image display device such as a liquid crystal display (LCD). Can do. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. In particular, a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application.

<Curing film, pattern forming method, color filter, and color filter manufacturing method>
Next, the cured film, the pattern forming method, and the color filter in the present invention will be described in detail through the manufacturing method.
The cured film of the present invention is formed by curing the colored composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, the colored composition of the present invention is applied onto a support to form a colored composition layer, and unnecessary portions are removed to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
The composition of the present invention may produce a color filter by pattern formation by a so-called photolithography method, or may form a pattern by dry etching.
That is, as a first production method of the color filter of the present invention, a step of applying a colored composition on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, A method for producing a color filter including a step of developing and removing an unexposed portion to form a colored pattern is exemplified.
Further, as a second production method of the color filter of the present invention, a step of applying a colored composition on a support to form a colored composition layer and curing to form a colored layer, a photo on the colored layer Production of a color filter comprising a step of forming a resist layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask A method is illustrated.
In the present invention, it is more preferable to manufacture by photolithography.
These details are described below.

  Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.

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

As a support that can be used in this step, for example, a solid-state imaging in which an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). An element 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. In the undercoat layer, a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like can be blended. Each of these components is derived from the components blended in the above-described composition of the present invention. It is preferable to select appropriately.

  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.

<Process for pattern formation by photolithography>
<< Exposure Step >>
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 more preferably 30mJ / cm ² ~1500mJ / cm ² is preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 is particularly preferred.

The film thickness of the cured film (colored 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 this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed. Although it exists, the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.

<< Development 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, trimethylbenzylammonium 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 hydrogencarbonate, sodium oxalate, sodium metaoxalate 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 to be formed, a cured film can be produced by sequentially repeating the above steps 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 coated film after development is in the above-described condition be able to.

<When patterning by dry etching>
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 a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type radiation sensitive composition is used. This positive type radiation sensitive composition includes a positive type photosensitive material sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition suitable for resist 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 resolution, it is used for manufacturing integrated circuits such as ICs and LSIs. 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 dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer containing the colorant. Combinations of solvents and alkaline aqueous solutions 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.

  Specifically, in the dry etching, the colored layer is dry etched using the resist pattern as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, etc. There are methods described in the publications.

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) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.

The mixed gas used in the first stage etching step 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. The second etching step and the over-etching step are performed in the first etching step after etching to a region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas. From the viewpoint of avoidance, 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. Preferably, they are monoethanolamine, diethanolamine, and triethanolamine, and more preferably 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 the stripping solution, it is sufficient that the resist pattern 52 formed on the first colored pattern 12 is removed, and a deposit as an etching product adheres to the side wall of the first colored pattern 12 However, the deposit may not be completely 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.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes 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.

Further, when the colored composition according to the present invention is used, for example, clogging of the nozzle of the coating device discharge section or the piping section, contamination due to adhesion, sedimentation, or drying of the colored composition or pigment in the coating machine may occur. is there. Therefore, in order to efficiently clean the contamination caused by the colored composition of the present invention, it is preferable to use the solvent relating to the present composition described above as a 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 also be suitably used for cleaning and removing the colored composition according to the present invention.
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 with respect to contaminants, a surfactant related to the present composition 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 of the present invention can be exposed with an excellent exposure margin, and the formed colored pattern (colored pixel) is excellent in pattern shape, and the surface of the pattern is not rough. Since the residue in the developing part is suppressed, the color characteristics are excellent.
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.

In addition, as a film thickness of the coloring pattern (color pixel) in the color filter of this invention, 2.0 micrometers or less are preferable, 1.0 micrometer or less is more preferable, and 0.7 micrometer or less is further more preferable.
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 above-described 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. .

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection 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 portion. It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

<Image display device>
The color filter of the present invention can be used not only for the solid-state imaging device but also for image display devices such as liquid crystal display devices and organic EL display devices, and is particularly suitable for use in liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.

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

The color filter of the present invention may be used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
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 multimer excellent in hue is used, the color purity, light transmittance, etc. are good and the color pattern (pixel) is excellent in color, so the resolution is high and the long-term durability is excellent. A COA 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, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

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. Regarding these components, 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)” Fuji Chimera Research Institute, Ltd., published 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.

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

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

Example of Synthesis of Dye Multimer The following xanthenes 1 to 4 are included in the preferred form (A1) of the dye multimer described above. The following xanthene 5 is included in the preferred form (A2) of the dye multimer described above. The following xanthene 6 is contained in the preferable form (A3) of the dye multimer described above. The following xanthenes 7 and 8 are included in the preferred form (A4) of the dye multimer described above.
<Synthesis of xanthene 1>

  After dissolving 125 g of chloroform in 20.0 g (41.8 mmol) of rhodamine B, 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling in an ice bath. Then, after cooling to 20 ° C. heated at an external temperature of 65 ° C. for 3 hours, 9.8 g (75.2 mmol) of 2-hydroxyethyl methacrylate was added while cooling in an ice bath, and 30.8 g (304 mmol) of triethylamine was added. did. After stirring for 3 hours at an internal temperature of 20 ° C., 100 g of chloroform was added and the mixture was separated with water, and then the chloroform layer was concentrated. The obtained concentrate was added to 100 mL of methanol, and 16.4 g (41.8 mmol) of trifluoromethylsulfonic acid tetrabutylammonium salt was added. Separation was performed with 200 mL of ethyl acetate and 100 mL of water, and the ethyl acetate layer was concentrated to obtain 18.0 g of monomer X.

  In a three-necked flask, monomer X (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) (23. 3 g) was added and heated to 80 ° C. under a nitrogen atmosphere. To this solution, monomer X (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2′-azobis (isobutyric acid) dimethyl) [trade name: V601, Wako Pure Chemical Industries, Ltd. (Mixed)] (0.58 g) and a mixed solution of PGMEA (23.3 g) were added dropwise over 5 hours. After stirring for 10 hours, the temperature was raised to 80 ° C., heating and stirring for 3 hours, and then allowed to cool to obtain an intermediate (MD-1) PGMEA solution. After cooling, the solution was added dropwise to a mixed solvent of methanol / ion exchange water = 100 mL / 10 mL to reprecipitate. After air drying at 40 ° C. for 2 days, 7.5 g of a dye multimer (xanthene 1) was obtained.

  The weight average molecular weight (Mw) of the dye multimer (xanthene 1) confirmed by GPC measurement was 10,700. Moreover, the acid value was 37 mgKOH / g by titration using 0.1N sodium hydroxide aqueous solution.

<Synthesis of xanthene 2 to xanthene 4>
A dye multimer (xanthene 2 to xanthene 4) was synthesized by performing the same operation except that the counter anion in the monomer X in Synthesis Example 1 was changed to that shown in the following table.

<Synthesis of xanthene 5>
The following monomers (67 mol% xanthene monomer and 33 mol% methacrylic acid) were copolymerized to synthesize xanthene 5.

  C. I. After dissolving 27.4 g (41.8 mmol) of Acid Red 289 and 125 g of chloroform, 9.6 g (62.6 mmol) of phosphorus oxychloride was added dropwise while cooling in an ice bath. Then, after cooling to 20 ° C. heated at an external temperature of 65 ° C. for 3 hours, 9.0 g (75.2 mmol) of 4-aminostyrene was added while cooling in an ice bath, and 30.8 g (304 mmol) of triethylamine was added. After stirring for 3 hours at an internal temperature of 20 ° C., 100 g of chloroform was added, and after liquid separation with water, 15.0 g of monomer Z was obtained by concentrating the chloroform layer. At this time, 10.0 g of monomer Z2 was obtained from the aqueous layer.

  Monomer Z (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), and PGMEA (23.3 g) were added to a three-necked flask and heated to 80 ° C. under a nitrogen atmosphere. To this solution, monomer Z (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2′-azobis (isobutyric acid) dimethyl) [trade name: V601, Wako Pure Chemical Industries, Ltd. Co., Ltd.] (0.58 g) and a mixed solution of PGMEA (23.3 g) were added dropwise over 4 hours. Then, after stirring for 4 hours, it heated up at 93 degreeC, after heating and stirring for 2 hours, it stood to cool and obtained the PGMEA solution of the intermediate body (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion exchange water = 100 mL / 10 mL to reprecipitate. After air drying at 40 ° C. for 2 days, 7.4 g of a dye multimer (xanthene 5) was obtained.

  The weight average molecular weight (Mw) of the dye multimer (xanthene 5) confirmed by GPC measurement was 10,000. Moreover, the acid value was 38 mgKOH / g by titration using 0.1N sodium hydroxide aqueous solution.

<Synthesis of xanthene 6>
Xanthene monomer Y 60mol% and methacrylic acid 40mol%

Rhodamine B 20.0 g (41.8 mmol) and the following polymerizable anion potassium salt 24.3 g (41.8 mmol) were salt-exchanged in 200 ml of methanol, 1 L of water was added, and the mixture was extracted with 500 ml of chloroform and concentrated. 25 g of Y was obtained.

  Monomer Y (8.2 g), methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), and PGMEA (23.3 g) were added to a three-necked flask and heated to 80 ° C. under a nitrogen atmosphere. To this solution, monomer Y (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2′-azobis (isobutyric acid) dimethyl) [trade name: V601, Wako Pure Chemical Industries, Ltd. (Mixed)] (0.58 g) and a mixed solution of PGMEA (23.3 g) were added dropwise over 5 hours. Thereafter, the mixture was stirred for 5 hours, heated to 93 ° C., heated and stirred for 2 hours, and then allowed to cool to obtain a PGMEA solution of intermediate (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion exchange water = 100 mL / 10 mL to reprecipitate. After air drying at 40 ° C. for 2 days, 4.8 g of a dye multimer (xanthene 6) was obtained.

  The weight average molecular weight (Mw) of the dye multimer (xanthene 6) confirmed by GPC measurement was 10,000.

<Synthesis of xanthene 7>
The following monomers (xanthene monomer Z2 (64 mol%) and methacrylic acid (36 mol%)) were copolymerized to synthesize xanthene 7.

  In a three-necked flask, monomer Z2 (8.2 g) obtained by synthesis of xanthene 5, methacrylic acid (0.46 g), dodecyl mercaptan (0.255 g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter “PGMEA”) (23.3 g) was added and heated to 80 ° C. under a nitrogen atmosphere. To this solution, monomer Z2 (8.2 g), methacrylic acid (1.075 g), dodecyl mercaptan (0.255 g), 2,2′-azobis (isobutyric acid) dimethyl) [trade name: V601, Wako Pure Chemical Industries, Ltd. Co., Ltd.] (0.58 g) and a mixed solution of PGMEA (23.3 g) were added dropwise over 3 hours. Then, after stirring for 4 hours, it heated up at 90 degreeC, after heating and stirring for 2 hours, it stood to cool and obtained the PGMEA solution of the intermediate body (MD-1). After cooling, the solution was added dropwise to a mixed solvent of methanol / ion exchange water = 100 mL / 10 mL to reprecipitate. After air drying at 40 ° C. for 2 days, 7.8 g of a dye multimer (xanthene 7) was obtained.

  The weight average molecular weight (Mw) of the dye multimer (xanthene 7) confirmed by GPC measurement was 11,000. Moreover, the acid value was 38 mgKOH / g by titration using 0.1N sodium hydroxide aqueous solution.

<Synthesis of xanthene 8>
(Copolymer of the following monomers)
According to the method for producing the salt-forming compound (A-1) described in paragraph 0165 of JP2011-242752A, a dye multimer (xanthene 8) was obtained. The weight average molecular weight (Mw) of the dye multimer (xanthene 7) confirmed by GPC measurement was 10,500.

Preparation of coloring composition Preparation of blue pigment dispersion Blue pigment dispersion 1 was prepared as follows.
C. I. Pigment Blue 15: 6 (9.6 parts (blue pigment, average particle size 55 nm)), Dispersbyk 111 (pigment dispersant) 3.2 parts, PGMEA 69.8 parts, and cyclohexanone 17.4 parts were mixed in a bead mill ( A pigment dispersion was prepared by mixing and dispersing with 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 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion 1 (CI Pigment Blue 15: 6 dispersion, pigment concentration 12.8% by mass) used in the coloring compositions of Examples and Comparative Examples.

・硬化性化合物（以下の構造の６官能モノマー、以下「ｍ１」と呼ぶ） １．４部

・光重合開始剤（以下の構造、以下「Ｉ−１」と呼ぶ、特開２０１１−１５８６５４号公報に記載） ０．８部

・色素多量体（キサンテン１、シクロヘキサノン１２．３％溶液）
２４．６部
・フッ素系界面活性剤（ＤＩＣ（株）製 Ｆ−７８１、ＰＧＭＥＡ１質量％溶液）
２．５部
・ＰＧＭＥＡ １６．２部
・エマルゲン４０８（花王製） ０．７部
・ｐ−メトキシフェノール ０．０１部 Preparation of Example 0 The following components were mixed and dispersed and dissolved to obtain a colored composition of Example 0.
Before adjusting Example 0, the solvent used was distilled and a drying agent was used to remove toluene and moisture in the system, and the dyes and pigments were washed with distilled water and dried to repeat Na, K ions were removed. Other materials such as monomers were refined before use and adjusted after removing impurities (toluene, Na, K ions, etc.).
-52.3 parts of the above blue pigment dispersion 1-Alkali-soluble resin 1 (a copolymer of 55 mol% of benzyl methacrylate and 45 mol% of methacrylic acid, weight average molecular weight 10,000, hereinafter referred to as "B1") 3 parts, alkali-soluble resin 2 (the following resin, weight average molecular weight 11,000, hereinafter referred to as “B2”) 0.2 part

Curing compound (hexafunctional monomer having the following structure, hereinafter referred to as “m1”) 1.4 parts

Photopolymerization initiator (the following structure, hereinafter referred to as “I-1”, described in JP 2011-158654 A) 0.8 part

・ Dye multimer (xanthene 1, cyclohexanone 12.3% solution)
24.6 parts · Fluorosurfactant (DIC Corporation F-781, PGMEA 1% by mass solution)
2.5 parts PGMEA 16.2 parts Emulgen 408 (manufactured by Kao) 0.7 parts p-methoxyphenol 0.01 parts

The result of having measured the density | concentration of the following components in the composition of Example 0 is shown. The water content was measured according to a known method by the Karl Fischer method. Specifically, the moisture content of the measurement material was measured using a Karl Fischer moisture meter (KF-06, manufactured by Mitsubishi Chemical Holdings Corporation), and the moisture content was measured as moisture content / mass of measurement material × 100.
Water content: 0.005 mass% or less Toluene concentration: 0.001 ppm or less Na ion concentration: 0.001 ppm or less K ion concentration: 0.001 ppm or less

  Samples of Examples 1 to 6 were prepared by adding water, toluene, a Na ion source (specifically NaCl), and a K ion source (specifically KCl) to the composition of Example 0.

硬化性化合物（モノマー（ｍ−３））

硬化性化合物（モノマー（ｍ−４））

The compositions of Examples 7 to 86 and Comparative Examples 1 to 16 were the same as Example 0 except that the dye multimer, the curable compound (monomer), and the photopolymerization initiator were changed as shown in the following table. A product was made.
Curable compound (monomer (m-2))

Curable compound (monomer (m-3))

Curable compound (monomer (m-4))

光重合開始剤（Ｉ−３、ＢＡＳＦ製Ｉｒｇａｃｕｒｅ９０７）

Photopolymerization initiator (I-2, OXE-02 manufactured by BASF)

Photopolymerization initiator (I-3, Irgacure 907 manufactured by BASF)

<Evaluation of long-term stability (viscosity)>
The initial viscosity (Vi) of the compositions obtained in the examples and comparative examples was measured and aged for 100 days in a sealed container at 5 ° C. Further, the viscosity (Vd) after aging was measured. A value of | Vi−Vd | / Vi × 100% was calculated, and evaluation was performed based on the value. The results are shown in the table below.
6: Viscosity change rate is 0.5% or less (particularly good)
5: Viscosity change rate is higher than 0.5% and 3% or less (good)
4: Viscosity change rate is higher than 3% and not higher than 7% (slightly good)
3: Viscosity change rate is higher than 7% and 8% or less (within allowable range)
2: Viscosity change rate is higher than 8% and not higher than 12% (outside the allowable range)
1: Viscosity change rate is higher than 12% (outside the allowable range)

Fabrication of color filter by coloring composition <Pattern formation>
Each of the colored compositions of Examples and Comparative Examples prepared as described above was coated on a glass substrate to form a colored composition layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 90 ° C. so that the dry film thickness of the coating film became 0.6 μm.

<Long light resistance under low oxygen concentration>
Made by Suga Test Instruments Co., Ltd., which is a light resistance tester for a xenon lamp light source (the oxygen supply is cut off and becomes a low oxygen state) by covering the film-formed product (pattern) obtained in Examples and Comparative Examples with a glass cover Using SX75F, a light resistance test was performed by irradiating with illuminance of 10,000 lux for 200 hours.
Evaluation was performed by measuring the color difference (ΔE * ab) before and after irradiation with MCPD-2000 manufactured by Otsuka Electronics Co., Ltd. The results are shown in the table below.
6: 0.5% or less (particularly good)
5: Higher than 0.5% and less than 1% (good)
4: 1% to 2% (slightly good)
3: More than 2% and less than 3% (within tolerance)
2: Higher than 3% and 5% or less (out of tolerance)
1: higher than 5% (out of tolerance)

<Defect assessment after long-term aging (foreign matter increase rate assessment)>
Each radiation-sensitive composition obtained above is applied on a silicon wafer so that the film thickness after application is 0.6 μm, and then heated at 100 ° C. for 2 minutes on a hot plate to give a colored composition. A material layer was obtained.
A foreign substance having a size of 1.0 μm or more was counted on the substrate on which the colored composition layer was formed, using a defect evaluation apparatus ComPLUS (manufactured by Applied Materials).
This evaluation was performed immediately after the preparation of the coloring composition and after 1 month of aging at 5 ° C., and the foreign matter increase rate was evaluated according to the following criteria.
The foreign matter increase rate was calculated by (the number of foreign matters after 1 month of refrigeration at 5 ° C./the number of foreign matters immediately after preparation). A criterion of 3 or more is desirable in practice. The results are shown in the table.
(Criteria)
6: Less than 1.1 5: 1.1 or more and less than 1.3 4: 1.3 or more and less than 1.5 3: 1.5 or more and less than 2.0 2: 2.0 or more and less than 3.0 1: 3. 0 or more

<Long-time evaluation>
(Production of silicon wafer with undercoat layer)
Resist CT-4000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; base clearing agent) is applied on a silicon wafer using a spin coater to a film thickness of 0.1 μm, and heated at 220 ° C. for 1 hour. An undercoat layer was formed by drying to obtain a silicon wafer with an undercoat layer.
(Preparation of colored pattern)
The coloring compositions of Examples and Comparative Examples were applied by spin coating on a silicon wafer with an undercoat layer so that the film thickness after application was 0.6 μm, and then on a hot plate at 90 ° C. for 2 minutes. A colored composition layer was obtained by heating.
Next, the obtained colored composition layer was exposed to an island pattern of 3.0 μm at 300 mj / cm ² through a mask using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Next, paddle development was performed on the colored composition layer after exposure using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water, and the coloring pattern was obtained.
The line width of the obtained colored pattern was observed using a length measurement SEM (trade name: S-7800H, manufactured by Hitachi, Ltd.). The difference between the maximum value and the minimum value of the line width within one pixel when the holding time was 72 hours was measured at 10 arbitrary points in the wafer to obtain an average value. Note that when the settling time was 0 hour, the average value was <0.02 μm in any of the examples and comparative examples.
(Criteria)
6: Less than 0.02 μm (best)
5: 0.02 μm or more and less than 0.04 μm (good)
4: 0.04 μm or more and less than 0.06 μm (slightly good)
3: 0.06 μm or more and less than 0.10 μm (within tolerance)
2: 0.10 μm or more and less than 0.20 μm (not acceptable)
1: 0.20 μm or more (Not acceptable (minimum))

<Defect evaluation after long-time moisture resistance test (foreign matter increase rate evaluation)>
The compositions of Examples and Comparative Examples were coated on a silicon wafer so that the film thickness after coating was 0.6 μm, and heated at 100 ° C. for 2 minutes on a hot plate to obtain a colored composition layer. It was. Thereafter, the entire surface was subjected to i-line exposure at an exposure amount of 1000 mJ / cm ² , and additional overheating was performed on a hot plate at 200 ° C./10 minutes to prepare an initial sample.
Regarding the initial sample, a sample subjected to moisture resistance under conditions of 85 ° C. and 85% RH for 408 hours was used as a sample after the moisture resistance test.
For each sample, a foreign substance having a size of 1.0 μm or more was counted using a defect evaluation apparatus ComPLUS (manufactured by Applied Materials). The foreign matter increase rate was evaluated according to the following criteria.
The foreign matter increase rate was calculated by (number of foreign matters in the sample after the moisture resistance test / number of foreign matters in the initial sample). A criterion of 3 or more is desirable in practice. The results are shown in the table.
(Criteria)
6: Less than 1.1 5: 1.1 or more and less than 1.3 4: 1.3 or more and less than 1.5 3: 1.5 or more and less than 2.0 2: 2.0 or more and less than 3.0 1: 3. 0 or more

<Cycle thermo test>
After the compositions of Examples and Comparative Examples were stored under the following temperature conditions, the rate of increase in coated foreign matter was evaluated.
Temperature condition (1): 45 ° C / 24H
Temperature condition (2): 23 ° C / 24H
Temperature condition (3): -18 ° C / 24H
After the test was repeated three times in the order of the temperature condition (1), the temperature condition (2), and the temperature condition (3), the coated foreign matter was evaluated.
<Evaluation of coated foreign matter>
The coloring composition was applied onto a silicon wafer so that the film thickness after application was 0.6 μm, and then heated at 90 ° C. for 2 minutes on a hot plate to obtain a coloring composition layer.
A foreign substance having a size of 2.0 μm or more was counted on the substrate on which the colored composition layer was formed, using a defect evaluation apparatus ComPLUS (manufactured by Applied Materials).
The foreign matter increase rate was calculated by (number of foreign matter after cycle thermo test / number of foreign matter immediately after preparation) and evaluated according to the following categories.
(Criteria)
6: Less than 1.1 (best)
5: 1.1 or more and less than 1.3 (good)
4: 1.3 or more and less than 1.5 (slightly good)
3: 1.5 or more and less than 2.0 (within tolerance)
2: 2.0 or more and less than 4.0 (not acceptable)
1: 4.0 or more (not acceptable)

From the results shown in the above table, it was found that the uniformity of the line width of the colored pattern can be maintained satisfactorily even when the toluene concentration in the colored composition is 0.001 to 10 ppm even if it is left for a long time. .
Further, it was found that when at least one of the sodium ion concentration and the potassium ion concentration in the coloring composition is 0.01 to 20 ppm, it is difficult to generate foreign matters when left in a low temperature environment for a long time.
Further, it was found that when the moisture content in the colored composition is 0.005 to 3 ppm, good light resistance can be maintained even when placed under a low oxygen concentration for a long period of time.
Moreover, in Examples 79-86, it turned out that all evaluation results other than evaluation of long-term stability over time are favorable.

Claims (10)

(A) a partial structure derived from a xanthene dye having a cation moiety and a dye multimer having an anion moiety, (B) a solvent, a curable compound having two or more terminal ethylenically unsaturated bonds, an alkali-soluble resin, A coloring composition containing a photopolymerization initiator,
The (A) dye multimer is a dye multimer containing a repeating unit represented by the general formula (a1-1),
The coloring composition whose toluene concentration in a coloring composition is 0.001-10 ppm.
Formula (a1-1)

(In General Formula (a1-1), X ¹ represents a group forming a main chain, L ¹ represents a single bond or a divalent linking group. DyeI represents a xanthene compound represented by Formula (J ′). (Denotes the derived partial structure.)

In the formula, 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, and m is 0 Represents an integer of ~ 5.   The coloring composition according to claim 1, wherein the water content in the coloring composition is 0.005 to 3 ppm. The anion moiety is a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, a tetraarylborate anion, B ⁻ (CN) _n1 (OR ^a ) _4-n1 (R ^a is an alkyl group having 1 to 10 carbon atoms or carbon Represents an aryl group having a number of 6 to 10, n1 represents 1 to 4) or PF _n2 R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms; The coloring composition of Claim 1 or 2 which represents the integer of 6. The anionic sites is bis (sulfonyl) imide anion or tris (sulfonyl) methide anion, colored composition according to claim 1 or 2. Furthermore, the coloring composition of any one of Claims 1-4 containing a phthalocyanine pigment. A coloring layer formed of a color filter, the coloring composition according to any one of claims 1-5. A step of applying the colored composition according to any one of claims 1 to 6 on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and an unexposed portion. And a step of forming a colored pattern by developing and removing the substrate. Applying the colored composition according to any one of claims 1 to 6 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 exposure and development to obtain a resist pattern; and a step of dry etching a colored layer using the resist pattern as an etching mask. A method for producing a solid-state imaging device, comprising the method for producing a color filter according to claim 7 or 8 . A method for manufacturing an image display device, comprising the method for manufacturing a color filter according to claim 7 or 8 .