WO2015001873A1

WO2015001873A1 - Colored curable composition, cured film using same, color filter, production method for color filter, solid state imaging element, liquid crystal display device, and organic el display device

Info

Publication number: WO2015001873A1
Application number: PCT/JP2014/064045
Authority: WO
Inventors: 陽祐村上; 貴規田口; 賢鮫島; 渡邉　哲也
Original assignee: 富士フイルム株式会社
Priority date: 2013-07-01
Filing date: 2014-05-28
Publication date: 2015-01-08
Also published as: JP6147224B2; JP2015028602A; KR20150143653A; KR101780993B1; TW201502211A

Abstract

Provided are: a colored curable composition capable of forming a colored layer having little occurrence of micro foreign matter; a cured film using same; a color filter; a production method for color filters; a solid state imaging element; a liquid crystal display device; and an organic EL display device. The colored curable composition includes: a coloring agent including a phthalocyanine halide dye; a heat-curable compound; a radical trapping agent; and a solvent that dissolves these.

Description

Colored curable composition, cured film using the same, color filter, method for producing color filter, solid-state imaging device, liquid crystal display device, and organic EL display device

The present invention relates to a colored curable composition, a cured film using the same, a color filter, a method for producing a color filter, a solid-state imaging device, a liquid crystal display device, and an organic EL display device.

The color filter is an indispensable component for the display of a solid-state image sensor or a liquid crystal display device. In order to form such a color filter, a colored curable composition is employed (for example, Patent Documents 1 to 7).

JP 2011-191383 A JP 2011-253174 A JP 2008-3551 A JP 2011-257591 A JP 2011-141534 A JP 2011-107430 A JP 2011-107429 A

In recent years, in order to reduce crosstalk (color mixing of light), it is required to make a color filter thin. Here, even if the color filter is thinned, it is required that the spectral wavelength shape remains the same. If it does so, it will be necessary to raise the density | concentration of the coloring agent in solid content in a colored curable composition significantly.
Further, a halogenated phthalocyanine that is a colorant is known as an excellent colorant. However, as a result of examination by the inventors of the present application, when halogenated phthalocyanine is used at a high concentration and under a thin film (1 μm or less), for example, the generation of minute foreign matter 1 as shown in FIG. It has been found that there is an impact on yield.
The present invention solves this problem, and is a colored curable composition capable of forming a colored layer with less generation of fine foreign matters, and particularly capable of forming a colored layer with less generation of fine foreign matters even when thinned. An object is to provide a curable composition.

As a result of the study by the present inventors under such circumstances, a colored layer in which the generation of minute foreign matters is reduced by blending a coloring agent containing a halogenated phthalocyanine dye and a radical trapping agent in the colored curable composition. It was found that can be formed.
The reason for this is presumed, but is considered as follows. When the radical trapping agent in the colored curable composition traps radicals, for example, as shown in FIG. 2, the halogen atom and phthalocyanine skeleton in the halogenated phthalocyanine dye 2 interact with the radical trapping agent 3. By reducing the aggregation of the halogenated phthalocyanine dye 2, it is considered that the generation of minute foreign matters can be suppressed.
For example, as shown in FIGS. 2 and 3, the halogenated phthalocyanine dye 2 has a smaller particle diameter than the halogenated phthalocyanine pigment 4. Therefore, the interparticle steric repulsion when the halogenated phthalocyanine dye 2 and the radical trapping agent 3 interact with each other is more effective when the halogenated phthalocyanine pigment 4 and the radical trapping agent 3 interact with each other. It is considered to be larger than Noh. As a result, the cohesive force change after the interaction between the halogenated phthalocyanine dye 2 and the radical trapping agent 3 appears more remarkably as compared with the case where the halogenated phthalocyanine pigment 4 is used, and the generation of minute foreign matters is further increased. It can be suppressed.
Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <18>.
<1> A colored curable composition comprising a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, a radical trapping agent, and a solvent for dissolving them.
<2> The colored curable composition according to <1>, wherein the radical trapping agent contains at least one compound containing at least one ring structure.
<3> The colored curable composition according to <1> or <2>, wherein the radical trapping agent includes at least one selected from a hindered amine compound, an ultraviolet absorber, and a thermal polymerization inhibitor.
<4> The colored curable composition according to any one of <1> to <3>, wherein the halogenated phthalocyanine dye is represented by the following general formula (1);

In the general formula (1), Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent,
At least one of the substituents is a halogen atom;
At least one other substituent is an aromatic group, a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), or a group represented by the following formula (2A). A group containing at least one functional group selected from a group to be selected, an amino group and a thiol group;
M represents two hydrogen atoms, metal atoms, metal oxides or metal halides;

In formula (1A), R ¹ represents an alkyl group having a fluorine atom;

In formula (2A), R ² and R ³ are each independently an alkyl group, and R ² and R ³ may be bonded to each other to form a ring.
<5> In the general formula (1), 1 to 8 of Z ¹ to Z ¹⁶ are
A group represented by the following general formula (1-2);
A group represented by the general formula (1-4), a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), and a group represented by the following formula (2A). A group containing at least one functional group selected from a group, an amino group, and a thiol group,
The colored curable composition according to <4>, which represents at least one selected from: General formula (1-2)

In general formula (1-2), X is an oxygen atom or a sulfur atom, and A ¹ is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. ; General formula (1-4)

In general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4.

In formula (1A), R ¹ represents an alkyl group having a fluorine atom;

In formula (2A), R ² and R ³ are each independently an alkyl group, and R ² and R ³ may be bonded to each other to form a ring.
<6> In the general formula (1), 1 to 8 of Z ¹ to Z ¹⁶ are
It represents a group represented by the following general formula (1-2) or a group represented by the following general formula (1-4), and at least one is a group represented by the general formula (1-2) Or
A group represented by the following general formula (1-2), a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), and a group represented by the following formula (2A) Represents a group containing at least one functional group selected from the group consisting of amino group and thiol group,
<4> or the colored curable composition according to <5>; general formula (1-2)

In general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4;

In formula (1A), R ¹ represents an alkyl group having a fluorine atom;

In formula (2A), R ² and R ³ are each independently an alkyl group, and R ² and R ³ may be bonded to each other to form a ring.
<7> The colored curable composition according to any one of <1> to <3>, wherein the halogenated phthalocyanine dye is represented by the following general formula (1-1): General formula (1-1)

In the general formula (1-1), Z ¹ to Z ¹⁶ are each a hydrogen atom, a halogen atom, a group represented by the following general formula (1-1-2), or a group represented by the following general formula (1-3). Or a group represented by the following general formula (1-4),
1 to 8 of Z ¹ to Z ¹⁶ represent a group represented by the following general formula (1-1-2) or a group represented by the following general formula (1-4),
At least one is a halogen atom, and at least one is a group represented by the following general formula (1-1-2);
M represents two hydrogen atoms, a metal atom, a metal oxide or a metal halide; general formula (1-1-2)

In general formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, and A ¹¹ is a phenyl group having 1 to 5 substituents R, or a naphthyl group having 1 to 7 substituents R. And the substituent R is represented by any one of the following general formulas (4) to (6): a nitro group, COOR ¹ , OR ² , a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms. Or a group selected from the following general formula (X); R ¹ is a group represented by the following general formula (1-3) or an alkyl group having 1 to 8 carbon atoms; R ² Is an alkyl group having 1 to 8 carbon atoms;

In general formula (4), R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents an optionally substituted diarylamino group, or an optionally substituted alkylarylamino group;
In the general formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, R ⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. A diarylamino group which may have a substituent, a substituent or an alkylarylamino group which may have a substituent;
In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, An arylcarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent;

In general formula (X), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
n1 represents an integer of 1 to 3; when n1 is 2 or 3, the plurality of R ¹¹ may be the same or different;
Y ¹ represents —O—, —S—, —NR ¹³ —, —SO ₂ —, or —C (═O) —. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R ¹² represents a monovalent substituent.
General formula (1-3)

In the general formula (1-3), R ³ represents an alkylene group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4; 1-4)

In general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4.
<8> 1 to 4 of Z ¹ to Z ¹⁶ are a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), or a group represented by the following formula (2A). The colored curable composition according to any one of <4> to <7>, which has at least one functional group selected from a group to be selected, an amino group, and a thiol group;

In formula (1A), R ¹ represents an alkyl group having a fluorine atom;

In formula (2A), R ² and R ³ are each independently an alkyl group, and R ² and R ³ may be bonded to each other to form a ring.
<9> The colored curable composition according to any one of <1> to <8>, wherein the colorant further contains a yellow pigment.
<10> The colored curable composition according to any one of <1> to <9>, wherein the thermosetting compound has two or more epoxy groups in one molecule.
<11> The colored curable composition according to any one of <1> to <10>, wherein the total content of the colorant is 60 to 90% by mass with respect to the total solid content of the colored curable composition.
<12> The colored curable composition according to any one of <1> to <11>, wherein the halogenated phthalocyanine dye is a multimer.
<13> A cured film obtained by curing the colored curable composition according to any one of <1> to <12>. <14> A color filter having a colored layer using the colored curable composition according to any one of <1> to <12>.
<15> The color filter according to <14>, wherein the colored layer has a thickness of 0.1 to 0.8 μm. <16> a step of curing a colored curable composition containing a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, a radical trapping agent, and a solvent for dissolving them to form a colored layer;
Forming a photoresist layer on the colored layer;
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 color filter, comprising:
<17> A liquid crystal display device, an organic electroluminescence device or a solid-state imaging device having the color filter according to <14> or <15>.
<18> A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging element having a color filter manufactured by the method for manufacturing a color filter according to <16>.

According to the present invention, it is possible to provide a colored curable composition capable of forming a colored layer with less generation of fine foreign matter, and particularly a colored curable composition capable of forming a colored layer with less generation of fine foreign matter even when thinned. It has become possible.

It is a figure which shows an example of the micro foreign material which exists in the colored layer obtained using the colored curable composition. It is a conceptual diagram for demonstrating a state when halogenated phthalocyanine dye and a radical trap agent interact. It is a conceptual diagram for demonstrating a state when a halogenated phthalocyanine pigment and a radical trap agent interact. It is a schematic sectional drawing which shows the structural example of a color filter and a solid-state image sensor.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes what has a substituent with what 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 the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
“Colored layer” means a pixel used in a color filter.
“Dye” means a coloring compound that is soluble in a specific solvent. Here, the specific solvent includes, for example, an organic solvent exemplified in the column of a solvent that dissolves at least a colorant containing a halogenated phthalocyanine dye described later, a thermosetting compound, and a radical trapping agent. Therefore, the pigment compound which dissolves in at least one of these solvents corresponds to the dye in the present invention.
“A solvent for dissolving a colorant, a thermosetting compound and a radical trapping agent containing a halogenated phthalocyanine dye” refers to, for example, a solvent for a colorant, a thermosetting compound and a radical trapping agent containing a halogenated phthalocyanine dye at 23 ° C. The solubility is 1% by mass or more, preferably 1% to 90% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 50% by mass.

Hereinafter, the colored curable composition, the color filter and the manufacturing method thereof, the solid-state imaging device, the liquid crystal display device and the organic EL display device of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

<Colored curable composition>
The colored curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) comprises a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, a radical trapping agent, and a solvent for dissolving them. Including. According to the present invention, it is possible to provide a colored curable composition capable of forming a colored layer with less generation of fine foreign matter, and particularly a colored curable composition capable of forming a colored layer with less generation of fine foreign matter even when thinned. it can. Thereby, the yield at the time of manufacturing a color filter can be improved.
Further, by using a halogenated phthalocyanine dye instead of a halogenated phthalocyanine pigment as a colorant, the luminance difference (distribution) in a fine area region due to the pigment particle size is reduced, and stable spectral performance can be maintained. it can.

<< Colorant >>
As the colorant, a halogenated phthalocyanine dye is essential and may contain other colorants, and preferably contains other colorants. The total amount of the colorant is preferably 65 to 85% by mass, more preferably 70 to 80% by mass with respect to the total solid content. According to the composition of the present invention, even when the content of the colorant with respect to the total solid content of the composition is increased, it is possible to form a colored layer with less generation of fine foreign matters, and thus the color filter can be thinned. . A halogenated phthalocyanine dye may be used individually by 1 type, and may be used together 2 or more types.
<< Halogenated phthalocyanine dye >>
The composition of the present invention comprises a halogenated phthalocyanine dye. The halogenated phthalocyanine dye refers to a compound having a phthalocyanine skeleton and having one or more halogen atoms as a substituent. In the present invention, it is preferable to have 4 to 15 halogen atoms in one molecule, more preferably 6 to 14, more preferably 8 to 14. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. A chlorine atom, a fluorine atom, or a bromine atom is preferable, a chlorine atom or a fluorine atom is more preferable, and a chlorine atom is further preferable.
The halogenated phthalocyanine dye used in the present invention is usually a compound having a maximum absorption wavelength in the region of 600 to 800 nm, and preferably having a maximum absorption wavelength in the region of 630 to 750 nm.

The halogenated phthalocyanine dye used in the present invention is preferably a compound represented by the following general formula (1).
General formula (1)

(In the general formula (1), Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one of the other substituents is aromatic. A group or a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), a group represented by the following formula (2A), an amino group and a thiol group. (M is a group containing one functional group, M represents two hydrogen atoms, metal atoms, metal oxides or metal halides.)

(In Formula (1A), R ¹ represents an alkyl group having a fluorine atom. In Formula (2A), R ² and R ³ are each independently an alkyl group, and R ² and R ³ are bonded to each other. And may form a ring.)

Here, in the general formula (1), Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ represent substituents substituted at eight α positions of the phthalocyanine nucleus. Therefore, these substituents are also referred to as α-position substituents. Similarly, Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ in the general formula (1) are substituents substituted at eight β-positions of the phthalocyanine nucleus. These substituents are also referred to as β-position substituents.
When the halogenated phthalocyanine dye is a phthalocyanine multimer to be described later, any of Z ¹ to Z ^{16 in} the compound represented by the general formula (1) preferably contains a multimeric structure.

Among the carboxyl group, epoxy group, aryl ester group, tertiary alkyl ester group, group represented by the above formula (1A), group represented by the above formula (2A), amino group and thiol group, Group, epoxy group, aryl ester group, tertiary alkyl ester group, group represented by the above formula (1A), group represented by the above formula (2A), amino group and thiol group are preferable, carboxyl group, epoxy group , An aryl ester group, a tertiary alkyl ester group, a group represented by the above formula (1A), and a group represented by the above formula (2A) are more preferable, a carboxyl group, an epoxy group, a tertiary alkyl ester group, and the above formula. The group represented by (2A) is more preferable.
The halogenated phthalocyanine dye used in the present invention usually contains the above functional group at the terminal portion of the structure. In the terminal part of the structure of the halogenated phthalocyanine dye, a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the above formula (1A), a group represented by the above formula (2A), amino By having at least one functional group selected from a group and a thiol group, the effects of the present invention can be achieved more effectively.

<<< Aryl ester group >>>
Examples of the aryl ester group include a substituted or unsubstituted aryl ester group and a substituted or unsubstituted heteroaryl ester group.
The aryl group contained in the aryl ester group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples include a phenyl group and a naphthyl group.
The heteroaryl group contained in the aryl ester group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is a single ring or a condensed ring, preferably a single ring or a condensed ring in which 2 to 8 rings are condensed, more preferably a single ring or a condensed ring in which 2 to 4 rings are condensed, A monocycle is more preferred.
The substituent of the aryl ester group is preferably an electron withdrawing group, for example, a nitro group, a methoxy group, a cyano group, a carboxyl group, a ketone group, an acyloxy group, a hydroxy group, a perfluoroalkyl group, an alkylsulfone group, an ethoxy group. , Isopropoxy group, t-butoxy group, benzyloxy group and the like.
As an aryl ester group used by this invention, what is represented by the following structure is preferable, for example.

In the structure of the aryl ester group, R represents a hydrogen atom or an electron-withdrawing group, and n represents an integer of 0 to 3. Examples of the electron-withdrawing group include the above-described electron-withdrawing group, and a nitro group and a perfluoroalkyl group (particularly, a trifluoromethyl group) are preferable. The substitution position of R may be any of the ortho-position, meta-position and para-position, but the para-position is preferred. n is preferably 0 or 1.

<<< Tertiary alkyl ester group >>
The tertiary alkyl ester group includes a substituted or unsubstituted tertiary alkyl ester group. Examples of the tertiary alkyl group in the tertiary alkyl ester group include a t-butyl group, a t-pentyl group, a t-hexyl group, and the like, and a t-butyl group and a t-pentyl group are particularly preferable.

<<< Group Represented by Formula (1A) >>>
The group represented by the above formula (1A) represents an alkyl group in which R ¹ has a fluorine atom in the above formula (1A).
The alkyl group having a fluorine atom is preferably an alkyl group having 2 or more fluorine atoms and a fluorine atom having 1 to 10 carbon atoms, which may be linear, branched or cyclic, A linear or branched one is preferred. The number of carbon atoms in the alkyl group having a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 4. The alkyl group having a fluorine atom preferably has a terminal structure of (—CF ₃ ). The alkyl group having a fluorine atom preferably has a fluorine atom substitution rate of 40 to 100%, more preferably 50 to 100%. Here, the substitution rate of fluorine atoms refers to the ratio (%) in which hydrogen atoms are substituted with fluorine atoms in alkyl groups having fluorine atoms.

<<< Group Represented by Formula (2A) >>>
In the group represented by the formula (2A), in the formula (2A), R ² and R ³ are each independently an alkyl group, and R ² and R ³ are bonded to each other to form a ring. May be.
In the above formula (2A), R ² and R ³ each independently may be a substituted or unsubstituted alkyl group, and are linear, branched, and R ² and R ³ are It may be any one of the rings bonded to each other. In particular, a linear or cyclic C3-C5 unsubstituted alkyl group in which R ² and R ³ are bonded to each other is preferable. When at least one of R ² and R ³ is a linear alkyl group, each of R ² and R ³ preferably independently has 1 to 5 carbon atoms, and has 1 to 4 carbon atoms. More preferably.
In particular, in the above formula (2A), R ² and R ³ are each independently a methyl group, an ethyl group, a propyl group, or a butyl group, or 4 carbon atoms in which R ² and R ³ are bonded to each other. A cyclic alkyl group of 6 to 6 is preferred.

<< Binding Form of Substituent Used in the Present Invention >>
The halogenated phthalocyanine dye used in the present invention has the above-described functional group, but this functional group may be directly bonded to the phthalocyanine skeleton of the halogenated phthalocyanine dye, or may be bonded through any linking group. It may be. For example, the form which the hydrogen atom of the substituent of the substituent T group mentioned later is substituted is mentioned.

In the general formula (1), Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one of the other substituents is an aromatic group. Is a group containing It is preferable to have 5 to 15 halogen atoms in one molecule, and more preferable to have 6 to 14 halogen atoms. As a halogen atom, a chlorine atom, a fluorine atom, or a bromine atom is preferable, a chlorine atom or a fluorine atom is more preferable, and a chlorine atom is further more preferable.
The aromatic group in the group containing an aromatic group (preferably a group represented by the general formula (1-2) described later) is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. The number of groups having an aromatic group is preferably 1 to 11 per molecule, more preferably 1 to 10, and even more preferably 2 to 7. Also preferred is an embodiment in which Z ¹ to Z ¹⁶ are all groups other than halogen atoms having an aromatic group.
The substituent is not particularly defined as long as the phthalocyanine compound does not lose its function as a dye, and examples thereof include substituent T described later.

In the general formula (1), 1 to 8 of Z ¹ to Z ¹⁶ are a group represented by the following general formula (1-2), a group represented by the general formula (1-4), a carboxyl group At least one functional group selected from a group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the above formula (1A), a group represented by the above formula (2A), an amino group, and a thiol group It is preferable to represent at least one selected from a group containing a group.
In particular, in the general formula (1), 1 to 8 of Z ¹ to Z ¹⁶ are represented by (i) a group represented by the following general formula (1-2) or a general formula (1-4). And at least one is a group represented by the general formula (1-2), or (ii) a group represented by the following general formula (1-2), and a carboxyl group, At least one functional group selected from an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), a group represented by the following formula (2A), an amino group, and a thiol group It preferably represents a containing group.
In the general formula (1), at least one of Z ¹ to Z ¹⁶ represents the general formula (1-2).
And, more preferably, 2 to 6 of Z ¹ to Z ¹⁶ are represented by the group represented by the general formula (1-2) or the general formula (1-4). And at least one is a group represented by the general formula (1-2).
Formula (1-2)

(In the general formula (1-2), X is an oxygen atom or a sulfur atom, and A ¹ is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. is there.)
General formula (1-4)

(In the general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4)

In the general formula (1-2), X is an oxygen atom or a sulfur atom, and preferably an oxygen atom. When X is an oxygen atom, the maximum absorption wavelength of the obtained phthalocyanine compound can be shifted to the short wavelength side.
A ¹ is a phenyl group which may have a substituent or a naphthyl group which may have a substituent, and is a phenyl group having 1 to 5 substituents or 1 to 7 substituents. And a phenyl group having 1 to 5 substituents is more preferable.

The group represented by the general formula (1-2) is more preferably a group represented by the following general formula (1-1-2).
Formula (1-1-2)

(In the general formula (1-1-2), X ¹ represents an oxygen atom or a sulfur atom, and A ¹¹ represents a phenyl group having 1 to 5 substituents R, or a naphthyl having 1 to 7 substituents R. The substituent R is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² is carbon An alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the general formulas (4) to (6), or a general formula ( Represents a group selected from X).)

(In the general formula (4), R ⁴ is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents a diarylamino group which may have a substituent or an alkylarylamino group which may have a substituent.
In the general formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, R ⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents a diarylamino group which may have a substituent, a substituent or an alkylarylamino group which may have a substituent.
In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, The arylcarbonyl group which may have a substituent, the alkylsulfonyl group which may have a substituent, and the arylsulfonyl group which may have a substituent are represented. )
Formula (X)

(In the general formula (X), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. N1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ are each Y ¹ may be —O—, —S—, —NR ¹³ — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —SO ₂ —, or And —C (═O) —, R ¹² represents a monovalent substituent.)

In general formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, preferably an oxygen atom. When X ¹ is an oxygen atom, the maximum absorption wavelength of the obtained phthalocyanine compound can be shifted to the short wavelength side.
A ¹¹ is a phenyl group having 1 to 5 substituents or a naphthyl group having 1 to 7 substituents, and more preferably a phenyl group having 1 to 5 substituents.

The number of substituents of the phenyl group is an integer of 1 to 5, but more preferably an integer of 1 to 3 from the viewpoint of the Gram extinction coefficient. When the substituent is a halogen atom, the number of substituents is 1 to 5 Any integer of is preferred. The number of substituents of the naphthyl group is an integer of 1 to 7, but from the viewpoint of the gram extinction coefficient (absorbance per gram), it is preferably an integer of 1 to 5, more preferably an integer of 1 to 3. 1 or 2 is more preferable.

The bonding position between the naphthyl group and X ¹ is not particularly limited, and may be any of the following 1-position (1-naphthyl group) or 2-position (2-naphthyl group).

Similarly, the bonding position of the substituent to the naphthalene ring is not particularly limited.
For example, when the bonding position of the naphthyl group and X ¹ is the 1-position (1-naphthyl group), the bonding position of the substituent to the naphthalene ring is the 2-position, 3-position, 4-position, 5-position, 6 However, in consideration of heat resistance and solvent solubility, the 2nd and 3rd positions are preferable, and the 2nd position is more preferable. When the bonding position between the naphthyl group and X ¹ is the 2-position (2-naphthyl group), the bonding positions of the substituent to the naphthalene ring are the 1-position, 3-position, 4-position, 5-position, 6-position, However, the 3rd and 6th positions are preferable, and the 3rd position is more preferable in consideration of heat resistance and solvent solubility.

The substituent R of the phenyl group or naphthyl group is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² Is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the general formulas (4) to (6), or It is a group selected from the formula (X).

When a plurality of substituents R are present in the phenyl group or naphthyl group, the plurality of Rs may be the same or different.
When the substituent R of the phenyl or naphthyl group is COOR ^1, R ¹ in the COOR ¹ is represented by an alkyl group substituted by 1 carbon atoms which may be 1-8 or the following general formula, (1-3) Represents a group.
General formula (1-3)

(In the general formula (1-3), R ³ represents an alkylene group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4)

When R ¹ is an alkyl group having 1 to 8 carbon atoms, the alkyl group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of solvent solubility. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl. And straight-chain, branched or cyclic alkyl groups such as n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Examples of the “substituent optionally present in the alkyl group having 1 to 8 carbon atoms” include an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group.
Examples of the alkyloxy group having 1 to 8 carbon atoms, which is a “substituent optionally present in an alkyl group having 1 to 8 carbon atoms”, include a methoxy group, an ethoxy group, an n-propyloxy group, an iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2- Examples include linear, branched or cyclic alkyloxy groups such as an ethylhexyloxy group. Among these, an alkyloxy group having 1 to 4 carbon atoms is preferable.
Examples of the halogen atom as the “substituent optionally present in the alkyl group having 1 to 8 carbon atoms” include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferable.
Examples of the aryl group that is a “substituent optionally present in an alkyl group having 1 to 8 carbon atoms” include a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, a p-chlorophenyl group, and the like. . Among these, a phenyl group is preferable. A plurality of these substituents may be present. When a plurality of these substituents are present, they may be the same or different, and even in the same case, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2.

When the substituent R of the phenyl group or naphthyl group is COOR ¹ and R ¹ is a group represented by the general formula (1-3), R ³ in the group represented by the general formula (1-3) is From the viewpoint of the effect on ether solvent solubility, 1 to 3 alkylene groups are preferred.
Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group.
R ⁴ in the group represented by the general formula (1-3) is an alkyl group of 1 to 8, more preferably an alkyl group of 1 to 4, from the viewpoint of molecular weight. Examples of the alkyl group having 1 to 8 carbon atoms include those described in the above R ¹ column. N in the group represented by the general formula (1-3) is an integer of 1 to 4, and preferably an integer of 1 to 3, from the viewpoint of molecular weight.

When the substituent R of the phenyl or naphthyl group is OR ^2, R ² in OR ² represents an alkyl group having 1 to 8 carbon atoms, preferably from the viewpoint of crystallinity and better handling property of the dye, a C1- 3 alkyl groups are shown.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include the same substituents as those described in R ¹ of COOR ¹ which is an example of the substituent R, and the preferred range is also synonymous.

When the substituent R of the phenyl group or naphthyl group is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom or an iodine atom is preferable. Among them, a chlorine atom and a fluorine atom are preferable because the molecular weight of the dye is reduced and the gram absorption coefficient is increased.

When the substituent R of the phenyl group or naphthyl group is an aryl group, examples of the aryl group include aryl groups such as a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among them, a phenyl group is preferable because the molecular weight of the dye is reduced and the gram extinction coefficient is increased.

When the substituent R of the phenyl group or naphthyl group is an alkyl group, examples of the alkyl group having 1 to 8 carbon atoms include the same substituents as those described in R ¹ of COOR ¹ as an example of the substituent R. The preferred range is also synonymous. Preferably, it is an alkyl group having 1 to 3 carbon atoms from the viewpoint of crystallinity of the dye and good handleability.
When the substituent R is an alkyl group, examples of the substituent that may be present in the alkyl group include a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and more preferably a fluorine atom or a chlorine atom. There may be a plurality of halogen atoms as substituents for the alkyl group, and when there are a plurality of halogen atoms, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3.

The case where the substituent R of the phenyl group or naphthyl group is a group selected from the above general formulas (4) to (6) will be described.
R ⁴ in the general formula (4) represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a substituted group A diarylamino group which may have a group or an alkylarylamino group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, A dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms, and a total carbon number. More preferred is a dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms in total, or an alkylarylamino group having 7 to 20 carbon atoms in total, and a diarylamino group having 12 to 20 carbon atoms in total or Dialkylamino groups of primes 2-20 is particularly preferred.
The alkyl moiety and the aryl moiety may further have a substituent, and the substituent is preferably an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group or a halogen atom, and an alkoxy group Are more preferable, and a methoxy group or an ethoxy group is more preferable. Moreover, the aspect which does not have a substituent is also preferable.

In the general formula (5), d represents an integer of 0 to 2, and R ⁵ is an alkyl group which may have a substituent when d is 0 or 1, or an aryl which may have a substituent. And when d is 2, the alkyl group which may have a substituent, the aryl group which may have a substituent, the dialkylamino group which may have a substituent, and the substituent Or a diarylamino group which may be substituted or an alkylarylamino group which may have a substituent. R ⁵ is preferably a dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms when d is 2.
The alkyl moiety and the aryl moiety may further have a substituent, and examples of the substituent include a substituent T described later. An alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. Or a halogen atom etc. are preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable. Moreover, the aspect which does not have a substituent is also preferable.

In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, An arylcarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 An aryl group having ˜20, an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms are preferable. An alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms are more preferable.
The alkyl moiety and the aryl moiety may further have a substituent, and examples of the substituent include a substituent T described later. An alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. Or a halogen atom etc. are preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable. Moreover, the aspect which does not have a substituent is also preferable. Examples of the alkyl group and the like which may have a substituent will be described later.

Preferred examples of the alkyl group that may have a substituent in the general formulas (4) to (6) are shown below. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, Hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, ethoxyethoxyethyl group, 2-chloroethyl group can be mentioned, more preferably methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, phenoxyethyl group, benzyl group, Phenylethyl group, N-butyl Examples thereof include aminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group. Particularly preferred are methyl group, ethyl group, propyl group, tert-butyl group, phenoxyethyl. Group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group and ethoxyethoxyethyl group.

Preferred examples of the aryl group which may have a substituent in the general formulas (4) to (6) are shown below. Such aryl groups include phenyl, 2-chlorophenyl, 2-methoxyphenyl, 4-butoxycarbonylphenyl, 4-N, N-dibutylaminocarbonylphenyl, 4-N-butylaminosulfonylphenyl 4-N, N-dibutylaminosulfonylphenyl group, more preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N-butylaminosulfonylphenyl group. 4-N, N-dibutylaminosulfonylphenyl group, particularly preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N, N-dibutylaminosulfonyl group. A phenyl group is mentioned.

Preferred examples of the dialkylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such a dialkylamino group include N, N-dimethylamino group, N, N-dibutylamino group, N, N-di (2-ethylhexyl) amino group, N-methyl-N-benzylamino group, N, N-di (2-ethoxyethyl) amino group, N.I. N-di (2-hydroxyethyl) amino group may be mentioned.

Preferred examples of the diarylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such a diarylamino group include an N, N-diphenylamino group, an N, N-di (4-methoxyphenyl) amino group, and an N, N-di (4-acylphenyl) amino group.

Preferred examples of the alkylarylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylarylamino group include an N-methyl-N-phenylamino group, an N-benzyl-N-phenylamino group, and an N-methyl-N- (4-methoxyphenyl) amino group.

Preferred examples of the alkylcarbonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylcarbonyl group include an acetyl group, a propylcarbonyl group, a heptyl-3-carbonyl group, a 2-ethylhexyloxymethylcarbonyl group, a phenoxymethylcarbonyl group, and a 2-ethylhexyloxycarbonylmethylcarbonyl group.

Preferred examples of the arylcarbonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such arylcarbonyl groups include benzoyl group, 4-methoxybenzoyl group, and 4-ethoxycarbonylbenzoyl group.

Preferred examples of the alkylsulfonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylsulfonyl group include a methanesulfonyl group, an octanesulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a phenoxypropylsulfonyl group.

Preferred examples of the arylsulfonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an arylsulfonyl group include a phenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 4-ethoxycarbonylphenylsulfonyl group.

Preferred examples of the alkylsulfonylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylsulfonylamino group include a methylsulfonylamino group, a butylsulfonylamino group, a hydroxypropylsulfonylamino group, a 2-ethylhexylsulfonylamino group, an n-octylsulfonylamino group, a phenoxyethylsulfonylamino group, and an allylsulfonylamino group. Is mentioned.

In the general formulas (4) to (6), examples of the vinylsulfonylamino group which may have a substituent include a vinylsulfonylamino group and a 1-methylvinylsulfonylamino group.

In the general formulas (4) to (6), the arylsulfonylamino group which may have a substituent includes a phenylsulfonylamino group, a p-methoxyphenylsulfonylamino group, a p-ethoxycarbonylsulfonylamino group, and the like. Is mentioned.
In the above general formulas (4) to (6), the alkylcarbonylamino group which may have a substituent is a methylcarbonylamino group, a 2-ethylhexanoylamino group, an n-heptylcarbonylamino group, an ethoxyethoxy group. Examples include a methylcarbonylamino group.

In the general formulas (4) to (6), examples of the arylcarbonylamino group which may have a substituent include a benzoylamino group, a 2-methoxybenzoylamino group, and a 4-vinylbenzoylamino group.

Examples of the substituent T are shown below.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having a carbon number of 2 to 18 alkenyl groups such as vinyl group, allyl group, 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group, naphthyl group), heterocyclic ring Group (preferably a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Limidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl Group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, , Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group) An aryloxy group (preferably having 6 to 2 carbon atoms) Aryloxy groups such as phenoxy group and 1-naphthoxy group, and heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 18 carbon atoms such as 1-phenyltetrazole-5-oxy group, 2- Tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably carbon number) An acyloxy group having 2 to 24, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, ethoxycarbonyloxy Tert-butoki In the case of a sicarbonyloxy group or a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, phenoxy Carbonyloxy group), carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl -N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group) Group), alkyls A phonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably an aryl having 6 to 24 carbon atoms) A sulfonyloxy group such as a phenylsulfonyloxy group, an acyl group (preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, a cyclohexanoyl group; Group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2,6-di-tert- Til-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group), a carbamoyl group (preferably a carbamoyl group having 1 to 24 carbon atoms) For example, carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN- Phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 24 or less carbon atoms, for example, amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group) , 2-ethylhexylamino group, cyclohexyl Amino group), anilino group (preferably 6 to 24 anilino group such as anilino group, N-methylanilino group), heterocyclic amino group (preferably 1 to 18 heterocyclic amino group such as 4-pyridylamino Group), a carbonamide group (preferably a carbonamide group having 2 to 24 carbon atoms, such as an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a ureido having 1 to 24 carbon atoms Group, for example, ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably an imide group having 24 or less carbon atoms, for example, N-succinimide group, N-phthalimide group), An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms) For example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably aryloxy having 7 to 24 carbon atoms) A carbonylamino group such as a phenoxycarbonylamino group, a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide Group, cyclohexanesulfonamido group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, for example, N, N-dipropylsulfamoylamino group, Ru-N-dodecylsulfamoylamino group), an azo group (preferably an azo group having 1 to 24 carbon atoms, for example, a phenylazo group, a 3-pyrazolylazo group), an alkylthio group (preferably having 1 to 24 carbon atoms). Alkylthio group, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably arylthio group having 6 to 24 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having carbon number) 1 to 18 heterocyclic thio groups such as 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably alkylsulfinyl group having 1 to 24 carbon atoms) For example, dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 24 carbon atoms) An arylsulfinyl group such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, such as phenylsulfonyl group, 1-naphthylsulfonyl group) Sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonic group Nyl group) and a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group).

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

The case where the substituent R of the phenyl group or naphthyl group is a group represented by the general formula (X) will be described.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
n1 represents an integer of 1 to 3, more preferably 1 or 2. When n1 is 2 or 3, the plurality of R ¹¹ may be the same or different.
Y ¹ represents —O—, —S—, —NR ¹³ —, —SO ₂ —, or —C (═O) —, and represents —O—, —SO ₂ —, or —C (═O). -Is preferred, and -O- or C (= O)-is more preferred. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ¹² represents a monovalent substituent, and examples of the substituent include the above-described substituent T. The substituent T may be further substituted with the substituent T. R ¹² is preferably an alkyl group which may have a substituent, an acyl group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent, Or an alkylamino group which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent. And an alkylamino group having 1 to 12 carbon atoms which may have a substituent.
The mass of the R ¹² portion per molecule is preferably 200 to 2500, and more preferably 250 to 1500.

When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

Next, general formula (1-4) will be described.
In the general formula (1-4), R ′ is an alkylene group having 1 to 3 carbon atoms from the viewpoint of ether solubility and molecular weight. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group.
R ″ is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms from the viewpoint of ether solubility and molecular weight. The alkyl group having 1 to 8 carbon atoms may be represented by the general formula: It is synonymous with R ³ in (1-3), and the preferred range is also synonymous.
n1 is an integer of 0 to 4, more preferably an integer of 1 to 2, from the viewpoint of ether solubility and molecular weight.

Next, M, which is the central part of the general formula (1), will be described. In the general formula (1), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. Examples of the metal atom include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal atom, a metal oxide or a metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper. , Vanadyl and zinc, more preferably zinc or copper, and particularly preferably copper. It is preferable that the central metal is zinc or copper because of high heat resistance. Further, it is particularly preferable that the central metal is zinc or copper because the solvent solubility in general-purpose solvents such as acetone, methanol, and methyl cellosolve is high, and the solubility in the resin is high and the contrast becomes high.

The compound represented by the general formula (1) is more preferably represented by the following general formula (1-1).
General formula (1-1)

(In the general formula (1-1), Z ¹ to Z ¹⁶ are each a hydrogen atom, a halogen atom, a group represented by the following general formula (1-1-2), or a general formula (1-3) Or a group represented by the following general formula (1-4), and 1 to 8 of Z ¹ to Z ¹⁶ are represented by the general formula (1-1-2)
Or a group represented by the general formula (1-4), at least one is a halogen atom, and at least one is a group represented by the general formula (1-1-2) It is. M represents two hydrogen atoms, a metal atom, a metal oxide or a metal halide. )

The general formula (1-1-2), the general formula (1-3), and the general formula (1-4) in the general formula (1-1) are represented by the general formula (1-1) described in the general formula (1). -2), synonymous with general formula (1-3) and general formula (1-4), and a preferred range is also synonymous. Therefore, Z ¹ to Z ¹⁶ in the general formula (1-1) are more preferably in the same range as ¹ to Z ^{16 in} the general formula (1).
M in the general formula (1-1) has the same meaning as M in the general formula (1), and a preferred range is also the same.

Examples of Z ¹ to Z ¹⁶ in the general formula (1) and general formula (1-1) used in the present invention will be given below, but the present invention is not limited to these.

Although the example of the phthalocyanine compound used by this invention is given to the following, it cannot be overemphasized that this invention is not limited to these. The following table shows the substituents represented by the following general formula and their numbers.

Ar in the following table represents the following structure.

In Table 1 above, Ph is a phenyl group.

In the abbreviations of the above compounds, Pc represents a phthalocyanine nucleus, Zn represents a central metal, a portion with “α-” represents a substituent at the α-position, and a portion with “β-” represents β Represents a substituent at the position.
x and y are numbers of 0 or more, where the number of substituents is 0 or more.

Since the phthalocyanine compound is a mixture having different substitution positions and substitution numbers, it is difficult to uniquely describe it as a structural formula. Further, the number of substitutions shown in the following table is a value obtained by approximating the average value of the number of substituents in the mixture, and may be a small number.

Moreover, although the following specific examples are also mentioned as a phthalocyanine dye used by this invention, this invention is not limited to these. For example, in the following specific examples G-1 to G-21 and G′-1 to G′-3, S-1 given as an example of Z ¹ to Z ¹⁶ described above is one of S-2 to S-47. It may be replaced with either one.
In the following general formula, R is the carboxyl group, epoxy group, aryl ester group, tertiary alkyl ester group, group represented by the above formula (1A), group represented by the above formula (2A), amino group And a substituent having at least one functional group selected from thiol groups and preferably bonded to the β-position. S represents another substituent which the phthalocyanine dye used in the present invention may have. X represents a halogen atom that the phthalocyanine dye used in the present invention may have.

<Method for producing halogenated phthalocyanine dye>
The method for producing the phthalocyanine dye used in the present invention is not particularly limited, and a conventionally known method can be used. A method of cyclizing a phthalonitrile compound and a metal salt in a molten state or in an organic solvent can be particularly preferably used. Hereinafter, preferred embodiments of the method for producing a phthalocyanine dye will be described. However, the present invention is not limited to the following preferred embodiments.
That is, the phthalonitrile compound (1) represented by the following formula (I),

A phthalonitrile compound (2) represented by the following formula (II):

A phthalonitrile compound (3) represented by the following formula (III):

And a phthalonitrile compound (4) represented by the following formula (IV):

These are cyclized with one selected from the group consisting of metal atoms, metal oxides, metal carbonyls, metal halides, and organic acid metals (also collectively referred to as “metal compounds” in this specification). Thus, a phthalocyanine compound can be produced.
In the above formulas (I) to (IV), Z ¹ to Z ¹⁶ are the desired phthalocyanine compounds (1)
Defined by the structure of Specifically, in the above formulas (I) to (IV), Z ¹ to Z ¹⁶ are the same as the definitions of Z ¹ to Z ^{16 in} the general formula (1), respectively. Omitted.

For the cyclization reaction, a conventionally known method such as the method described in JP-A No. 64-45474 can be used.
In the above embodiment, the cyclization reaction is carried out by melting one kind selected from the group consisting of the phthalonitrile compounds of formulas (I) to (IV) and a metal, a metal oxide, a metal carbonyl, a metal halide and an organic acid metal in a molten state or It is preferable to react in a solvent. The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal that can be used at this time are those corresponding to the central part of the phthalocyanine compound obtained after the reaction (M in the general formula (1)). If there is, there is no particular limitation. Therefore, metals such as iron, copper, zinc, vanadium, titanium, indium and tin listed in the item M in the above general formula (1), metal halides such as chlorides, bromides and iodides of these metals, Examples thereof include metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, complex compounds such as acetylacetonate, and metal carbonyls such as carbonyl iron. Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium and tin; metal halides such as chloride, bromide, iodide, etc. of this metal, such as vanadium chloride, titanium chloride, chloride Copper, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, iodide Aluminum, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, three Iron dioxide, triiron tetroxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide Metal oxides such as cobalt dioxide, cuprous oxide, cuprous oxide, cupric oxide, copper trioxide, barium oxide, zinc oxide, germanium monoxide, and germanium dioxide; copper acetate, zinc acetate, cobalt acetate, copper benzoate And organic acid metals such as zinc benzoate; and complex compounds such as acetylacetonate and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Of these, metals, metal oxides and metal halides are preferable, metal halides are more preferable, vanadium iodide, copper iodide and zinc iodide are more preferable, and iodine is particularly preferable. Copper iodide and zinc iodide, most preferably zinc iodide. When zinc iodide is used, the central metal is zinc. Among metal halides, it is preferable to use iodide because it has excellent solubility in solvents and resins, and the spectrum of the resulting phthalocyanine compound is sharp and easily fits within the desired wavelength range of 640 to 750 nm. is there. The detailed mechanism of sharpening the spectrum when using iodide during the cyclization reaction is unknown, but when iodide is used, the iodine remaining in the phthalocyanine compound after the reaction may have some interaction with the phthalocyanine compound. It is presumed that iodine is present between the layers of the phthalocyanine compound due to the action. However, the mechanism is not limited to the above mechanism. In order to obtain the same effect as when metal iodide is used for the cyclization reaction, the obtained phthalocyanine compound may be treated with iodine.

Moreover, in the said aspect, although a cyclization reaction can be performed even without a solvent, it is preferable to carry out using an organic solvent. The organic solvent may be any inert solvent that has a low reactivity with the phthalonitrile compound as a starting material, and preferably exhibits no reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol; and pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, Triethylamine, tri n- butylamine, dimethyl sulfoxide, aprotic polar solvents such as sulfolane.
Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and 1-octanol, dichlorobenzene and benzonitrile are more preferably used. These solvents may be used alone or in combination of two or more.

The reaction conditions for the phthalonitrile compound of the formulas (I) to (IV) and the metal compound in the above embodiment are not particularly limited as long as this reaction proceeds. On the other hand, the total amount of the phthalonitrile compounds of the above formulas (I) to (IV) is 1 to 500 parts by weight, preferably 10 to 350 parts by weight, and the metal compound is 4 moles of the phthalonitrile compound. The charge is preferably in the range of 0.8 to 2.0 mol, more preferably 0.8 to 1.5 mol. The reaction temperature during cyclization is not particularly limited, but is preferably in the range of 30 to 250 ° C., more preferably 80 to 200 ° C. The reaction time is not particularly limited, but is preferably 3 to 20 hours. After the reaction, a phthalocyanine compound that can be used in the next step can be efficiently and highly purified by filtration, washing, and drying according to a conventionally known method for synthesizing phthalocyanine compounds.

In the above embodiment, the starting phthalonitrile compounds of formulas (I) to (IV) can be synthesized by a conventionally known method, or commercially available products can also be used.

<Halogenated phthalocyanine multimer>
The halogenated phthalocyanine dye used in the present invention may be a multimer (halogenated phthalocyanine multimer). In the present specification, a multimer is a compound containing two or more halogenated phthalocyanine structures, and includes a structure such as a dimer, trimer or polymer.

The halogenated phthalocyanine multimer is a halogenated phthalocyanine multimer comprising at least one of structural units represented by the following general formula (A), general formula (B), and general formula (C), or general A halogenated phthalocyanine multimer represented by the formula (D) is preferred.
Structural unit represented by general formula (A)

In general formula (A), X ¹ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. DyeI represents a structure containing a halogenated phthalocyanine skeleton.

In the above general formula (A), X ¹ represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but is particularly preferably a linking group represented by the following (XX-1) to (X-24): 1) (meth) acrylic linking chains represented by (XX-2), styrene linking chains represented by (XX-10) to (XX-17), and (XX-24) More preferably, it is a vinyl type connecting chain. In (XX-1) to (X-24), it is linked to L ₁ at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In general formula (A), L ¹ represents a single bond or a divalent linking group. In the case where L ₁ represents a divalent linking group, the divalent linking group may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene group). Etc.), substituted or unsubstituted arylene groups having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking groups, —CH═CH—, —O—, —S— , —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof. Represents. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In the general formula (A), DyeI represents a structure containing a halogenated phthalocyanine skeleton, that is, a partial structure derived from a halogenated phthalocyanine in a halogenated phthalocyanine multimer.
When DyeI is a structure derived from the compound represented by the general formula (1), any ^one of Z ¹ to Z ^{16 in} the compound represented by the general formula (1) is It is preferably bonded to L ¹ .
For details of the general formula (A), paragraphs 0138 to 0152 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.

Structural unit represented by general formula (B)

In general formula (B), X ² has the same meaning as X ¹ in general formula (A). L ² has the same meaning as L ¹ in the general formula (A). Y ² represents a group capable of ionic bonding or coordination bonding with DyeII. DyeII represents a structure containing a halogenated phthalocyanine skeleton.

In general formula (B), X ² has the same meaning as X ² in general formula (A), and the preferred range is also the same. L ² has the same meaning as L ¹ in the general formula (A), and the preferred range is also the same. Y ² may be any group capable of ionic bonding or coordination bonding with Dye II, and may be either an anionic group or a cationic group. Examples of the anionic group include COO ⁻ , PO ₃ H ⁻ , SO ₃ ⁻ , —SO ₃ NH ⁻ , —SO ₃ N ⁻ CO— and the like, and COO ⁻ , PO ₃ H ⁻ and SO ₃ ⁻ are preferable. .
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.
Y ² can be bonded to an anion part (COO ⁻ , SO ₃ ⁻ , O ⁻ etc.) or a cation part (the onium cation, metal cation etc.) of DyeII.
When DyeII has a structure derived from the compound represented by the general formula (1) described above, any ^one of Z ¹ to Z ^{16 in} the compound represented by the general formula (1) is present in the general formula (B). It is preferably bonded to Y ^{2 of}
For details of the general formula (B), paragraphs 0156 to 0161 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

Structural unit represented by general formula (C)

In general formula (C), L ³ represents a single bond or a divalent linking group. DyeIII represents a structure containing a halogenated phthalocyanine skeleton. m represents 0 or 1;

In the general formula (C), the divalent linking group represented by L ³ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, 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—, Preferred examples include —SO ₂ — and a linking group formed by linking two or more of these. m represents 0 or 1, but is preferably 1.
When DyeIII has a structure derived from the compound represented by the above general formula (1), any ^one of Z ¹ to Z ^{16 in} the compound represented by the general formula (1) is represented in the general formula (C). it is preferred that the of L ³ are bound.

It describes a specific example which is suitably used as the divalent linking group represented by L ³ in the general formula (C) below, but not limited to as L ³ of the present invention.
For details of the general formula (C), paragraphs 0165 to 0167 of JP2013-29760A can be referred to, the contents of which are incorporated herein.

Halogenated phthalocyanine multimer represented by the general formula (D)

(In general formula (D), L ⁴ represents an n-valent linking group. N represents an integer of 2 to 20. When n is 2 or more, the structures of DyeIV may be the same or different. DyeIV represents a structure containing a halogenated phthalocyanine skeleton.)
In the above general formula (D), n is preferably 3 to 15, particularly preferably 3 to 6.
In the general formula (D), 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 (eg, methylene group, 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—, — Preferable examples include SO ₂ — and a linking group formed by linking two or more of these.

An 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 heterocyclic linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.
When DyeIV has a structure derived from the compound represented by the above general formula (1), any ^one of Z ¹ to Z ^{16 in} the compound represented by the general formula (1) is represented in the general formula (D). it is preferred that the of L ⁴ are attached.

Specific examples of L ⁴ in the general formula (D) are shown below, but the present invention is not limited thereto.
For details of the general formula (D), paragraphs 0173 to 0178 of JP2013-29760A can be referred to, the contents of which are incorporated herein.

A halogenated phthalocyanine multimer having a structural unit represented by any one of general formula (A), general formula (B) and general formula (C), and a halogenated phthalocyanine large amount represented by general formula (D) The halogenated phthalocyanine multimer having a structural unit represented by general formula (A) and general formula (C) and the halogenated phthalocyanine multimer represented by general formula (D) are linked by a covalent bond. Therefore, the colored curable composition containing the halogenated phthalocyanine multimer is excellent in heat resistance, and when the colored curable composition is applied to the formation of a colored pattern of multiple colors, This is preferable because it is effective in suppressing color migration. In particular, the compound represented by the general formula (A) is preferable because the molecular weight of the halogenated phthalocyanine multimer is easily controlled.

The halogenated phthalocyanine multimer may have another functional group in the structural portion including the halogenated phthalocyanine skeleton of the above-described halogenated phthalocyanine multimer. Examples of other functional groups include polymerizable groups, acid groups, and alkali-soluble groups (for example, carboxylic acid, sulfonic acid, phosphoric acid, and phenolic hydroxyl group).
Moreover, the halogenated phthalocyanine multimer may contain other repeating units in addition to the repeating unit including the structure containing the halogenated phthalocyanine skeleton described above. Other repeating units may have a functional group. 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 halogenated phthalocyanine multimer may have other repeating units in addition to the repeating units represented by the general formulas (A) to (D). One type of other repeating unit may be contained in one halogenated phthalocyanine multimer, or two or more types may be contained.
The halogenated phthalocyanine multimer may have other functional groups in the halogenated phthalocyanine multimer represented by the general formulas (A) to (D).

The halogenated phthalocyanine 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, a structure containing a halogenated phthalocyanine skeleton may contain a polymerizable group, or may contain other parts. In the present invention, the structure containing a halogenated phthalocyanine skeleton preferably contains a polymerizable group.
Moreover, in this invention, the aspect in which other parts other than the structure containing a halogenated phthalocyanine skeleton contain a polymeric group is also preferable.
As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, an acid, or heat can be used. Examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), and a methylol group. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, and a (meth) acryloyl group derived from glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate is more preferable.
The halogenated phthalocyanine multimer is preferably a polymer having a repeating unit derived from a halogenated phthalocyanine compound having one radical polymerizable group.

It is also preferred that the halogenated phthalocyanine multimer has an epoxy group. Examples of the halogenated phthalocyanine multimer having an epoxy group include a repeating unit derived from a halogenated phthalocyanine compound having one radical polymerizable group and a radical polymerizable monomer having an epoxy group (for example, glycidyl acrylate, glycidyl methacrylate, etc.). Examples thereof include a polymer having a repeating unit derived therefrom.

As a method for introducing a polymerizable group, for example, paragraphs 0180 to 0188 in JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
For example, a method of obtaining a halogenated phthalocyanine multimer having an ethylenically unsaturated double bond is obtained by radicalizing a monomer mixture containing a halogenated phthalocyanine compound having one radical polymerizable group and a radical polymerizable monomer having a reactive group. The method of adding the compound which reacts with a reactive group and the compound which has an ethylenically unsaturated double bond with respect to the polymer obtained by superposition | polymerization is mentioned.
Examples of the reactive group include a carboxyl group and a hydroxy group. Examples of the radical polymerizable monomer having a reactive group include acrylic acid, methacrylic acid, hydroxyethyl acrylate, and hydroxyethyl methacrylate.
Examples of the group that reacts with the reactive group include an epoxy group and an isocyanate group.
Examples of the compound having an ethylenically unsaturated double bond include glycidyl acrylate, glycidyl methacrylate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like.

The amount of polymerizable groups possessed by the halogenated phthalocyanine multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and more preferably 0.3 to 1. More preferably, it is 0 mmol.

The weight average molecular weight of the halogenated phthalocyanine multimer is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and further preferably 4,000 to 10,000. preferable. The weight average molecular weight / number average molecular weight ratio of the halogenated phthalocyanine multimer is preferably 1.0 to 3.0, more preferably 1.6 to 2.5, and more preferably 1.6 to 2 More preferably, it is 0.0. The weight average molecular weight and degree of dispersion of the polymer are defined as polystyrene conversion values by GPC measurement. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super Super AWM-H (Tosoh Corporation) as a column. 6.0 mm ID × 15.0 cm can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

The blending amount of the halogenated phthalocyanine dye in the composition of the present invention is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and more preferably 40 to 50% by mass with respect to the total solid content. % Is more preferable.
In the colorant contained in the composition of the present invention, the blending amount of the halogenated phthalocyanine dye is preferably 55 to 80% by mass, more preferably 60 to 75% by mass.
The blending amount of the phthalocyanine compound containing no halogen atom in the composition of the present invention is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total solid content. By setting it as such a range, the effect of this invention is exhibited more effectively.

<Radical trapping agent>
The composition of the present invention contains a radical trapping agent. A radical trap agent may be used individually by 1 type, and may be used together 2 or more types.
The radical trapping agent in the present invention preferably has at least one ring structure. When the radical trapping agent has a ring structure, it is presumed that the steric bulk of the radical trapping agent promotes the interparticle steric repulsion ability when the halogenated phthalocyanine dye interacts with the radical trapping agent. Moreover, when the ring structure of the radical trapping agent is oriented horizontally with respect to the phthalocyanine ring, it is presumed that the inhibitory effect on the TT-TT interaction (stacking) between phthalocyanines is also great.
The composition of the present invention preferably contains at least one selected from a naphthalene derivative, a thioether compound, a hindered amine compound, an ultraviolet absorber, and a thermal polymerization inhibitor as a radical trapping agent. In particular, the composition of the present invention more preferably contains at least one selected from a hindered amine compound, an ultraviolet absorber and a thermal polymerization inhibitor as a radical trapping agent.

Examples of naphthalene derivatives include naphthohydroquinone compounds such as naphthohydroquinone sulfonate onium salts, and the like, and 1,4-dihydroxynaphthalene, 6-amino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4 -Dione, 6-methylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-ethylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione 6-propylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-butylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, -(Α, α-dimethyl) naphthalene, 2- (α, αdimethylbenzyl) naphthalene, 2-t-amylnaphthalene , 2-trimethylsilyl -1,4,5,8, - dimethyl-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. Among these, 1,4-dihydroxynaphthalene is particularly preferable.

The thioether compound is not particularly limited as long as it is a compound having at least one thioether group in the molecule, for example. For example,

dimethyl

3,3′-thiodipropionate, dihexylthiodipropionate, dinonylthiodipropionate, didecylthiodipropionate, diundecylthiodipropionate, didodecylthiodipropionate, ditridecylthio Dipropionate, Ditetradecylthiodipropionate, Dipentadecylthiodipropionate, Hexadecylthiodipropionate, Diheptadecylthiodipropionate, Dioctadecylthiodipropionate, Dihexylthiodibutyrate, Dinonylthio Dibutyrate, Didecylthiodibutyrate, Diundecylthiodibutyrate, Didodecylthiodibutyrate, Ditridecylthiodibutyrate, Ditetradecylthiodibutyrate, Dipentadecylthiodibutyrate, Hexadecylthiodi Chireto, 3-methoxy-2- [2- [cyclopropyl- (3-fluorophenyl) methyl thio methyl] phenyl] methyl acrylate, di heptadecyl thio dibutyrate and the like. Of these, dimethyl 3,3'-thiodipropionate is particularly preferred.

Examples of the hindered amine compound include compounds having a partial structure represented by the following formula (RT1).
Formula (RT1)

(In Formula (RT1), R ¹ to R ⁴ each independently represents a hydrogen atom or an alkyl group, and R ⁵ represents an alkyl group, an alkoxy group, or an aryloxy group.)
As the alkyl group, a linear alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. The alkyl group used for the alkoxy group is preferably a linear alkyl group having 1 to 4 carbon atoms. Examples of the aryl group used for the aryloxy group include a phenyl group and a naphthyl group.
Further, the molecular weight of the hindered amine compound is preferably 2000 or less, and more preferably 1000 or less. In view of easy availability in the market, the molecular weight of the hindered amine compound is preferably 400 to 700.
As such a hindered amine compound, commercially available TINUVIN123, TINUVIN144, TINUVIN152 manufactured by BASF, Adeka Stub LA-52 manufactured by Adeka, and the like can be preferably used.

Examples of the ultraviolet absorber include salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, and the like, and benzotriazole compounds are preferred.
Examples of benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- (2′-hydroxy-5 ′). -Merphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like. Among these, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol is particularly preferable. Examples of commercially available benzotriazole compounds include TINUVIN900, TINUVIN928, TINUVINP, TINUVIN234, TINUVIN326, and TINUVIN329 manufactured by BASF.
Other ultraviolet absorbers that can be used in the present invention include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 '-Hydroxybenzoate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2' -Hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-piperidine) -sebacate, 4-hydroxy-2,2,6,6-tetramethylpiperidine Condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidine) S Le, 7 - {[4-chloro-6- (diethylamino) -1,3,5-triazin-2-yl] amino} -3-phenyl coumarin, and the like.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, phenothiazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] and the like, and at least one selected from p-methoxyphenol and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is used. It is preferable.
As a commercially available product, for example, ADK STAB AO-60 manufactured by ADEKA Corporation can be used.

In addition to the radical trapping agent described above, the composition of the present invention includes an oxidizing agent described in paragraphs 0183 to 0210 of JP2011-141534A, and paragraphs 0103 to 0153 described in JP2011-253174A. A polymerizable compound having a radical scavenging ability (for example, a hindered amine type or a hindered phenol type polymerizable compound) or the like can be used, and the contents thereof are incorporated in the present specification.

The blending amount of the radical trapping agent in the composition of the present invention is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and more preferably 3 to 10% by mass with respect to the total solid content. It is particularly preferred that
The molar ratio of the radical trapping agent to the halogenated phthalocyanine dye in the composition of the present invention is preferably 0.1 to 5, and more preferably 0.2 to 1.

<Other colorants>
The composition of the present invention may contain other colorants in addition to the halogenated phthalocyanine compound, and preferably contains other colorants. As the other colorant, a yellow pigment is preferably used, and it may be a dye, a pigment, or a mixed system of a dye and a pigment. Other colorants may be used alone or in combination of two or more.

Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

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

1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
These organic pigments can be used alone or in various combinations in order to increase color purity.

When the colorant is a dye, a colored curable composition in a state of being uniformly dissolved in the composition can be obtained. There is no restriction | limiting in particular as dye, A well-known dye can be used for conventional color filters.
Examples of the chemical structure include azo series (for example, CI solvent yellow 162) and methine series (CI solvent yellow 93).
As the methine dye, a monomethine dye is preferable, and a monomethine dye represented by the following general formula (5) is more preferable.

(In General Formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an aromatic ring group having a substituent.)
R ¹¹ is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
R ¹² is preferably a phenyl group or a naphthyl group, and the substituent is preferably an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinylcarbonylamino group, or an arylcarbonylamino group. An alkylsulfonylamino group is preferred. The alkyl group having 1 to 12 carbon atoms may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.

Moreover, as a coloring agent, an acid dye and / or a derivative thereof may be suitably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

Specific examples of the acid dye are shown below, but are not limited thereto. For example, the following can be mentioned.
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow

2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Food Yellow 3;

Modern Yellow

5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
And derivatives of these dyes.

The yellow dye used in the present invention is particularly preferably an azo dye and / or a methine dye, and more preferably an azo dye.

<Pigment dispersion>
When a pigment is used for preparing the composition of the present invention, it is preferably a pigment dispersion. From the viewpoint of improving the dispersibility of the pigment, it is preferable to add a pigment dispersant.

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], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant acts to prevent re-aggregation of the pigment by adsorbing on the surface of the pigment. Therefore, as the pigment dispersant, a terminal-modified polymer having an anchor site to the pigment surface, a graft polymer, and a block polymer can be mentioned as preferred structures.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

The pigment dispersant that can be used in the present invention is also available as a commercial product. Specific examples include the following.
“Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group)”, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 manufactured by BYK Chemie (Polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050-4010-4165 (polyurethane) ”, EFKA 4330-4340 (block copolymer) manufactured by EFKA 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fan Techno Co., Ltd. Made by Addis -PB821, PB822 "," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd.," Polyflow No. 50E, No. 300 (acrylic copolymer) "," Disparon KS-860, 873SN "manufactured by Enomoto Kasei Co., Ltd. , 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725, “Demol RN, N (naphthalenesulfonic acid formalin) manufactured by Kao Corporation Polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxy) Ethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”, Lube “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000, 32000, 38500 (graft) Type polymer), “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)” manufactured by Nikko Chemical.

In addition, a dispersant described in paragraphs 0028 to 0124 of JP2011-070156A and a dispersant described in JP2007-277514A are preferably used, and the contents thereof are incorporated in the present specification.

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 content of the pigment dispersant in the composition of the present invention is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the pigment, and 10 to 60 parts by mass. More preferably.
Specifically, when a polymer dispersant is used, the amount thereof 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 in the range of 10 to 80 parts by mass. It is more preferable that
When the pigment derivative is used in combination, the amount of the pigment derivative used is preferably in the range of 1 to 30 parts by mass, preferably in the range of 3 to 20 parts by mass, with respect to 100 parts by mass of the pigment. Is more preferable, and the range of 5 to 15 parts by mass is particularly preferable.

-Pigment derivatives-
When the colorant contains a pigment, it is preferable to further contain a pigment derivative in order to increase the adsorptivity of the dispersion resin to the pigment. The pigment derivative is a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. The pigment derivative preferably contains an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.

Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.

As the pigment derivative, quinoline-based, benzimidazolone-based and isoindoline-based pigment derivatives are particularly preferable, and quinoline-based and benzimidazolone-based pigment derivatives are more preferable. A pigment derivative having a structure represented by the following general formula (P) is particularly preferred.

General formula (P)

In the general formula (P), A represents a partial structure selected from the following general formulas (PA-1) to (PA-3). B represents a single bond or a (t + 1) -valent linking group. C represents a single bond, —NH—, —CONH—, —CO ₂ —, —SO ₂ NH—, —O—, —S— or SO ₂ —. D represents a single bond, an alkylene group, a cycloalkylene group or an arylene group. E represents —SO ₃ H, —SO ₃ M (M represents an alkali metal atom), —CO ₂ H or N (Rpa) (Rpb). Rpa and Rpb each independently represents an alkyl group or an aryl group, and Rpa and Rpb may be linked to each other to form a ring. t represents an integer of 1 to 5.

In the general formulas (PA-1) and (PA-2), Rp1 represents an alkyl group having 1 to 5 carbon atoms or an aryl group. In General Formula (PA-3), Rp2 represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. s represents an integer of 1 to 4. When s is 2 or more, the plurality of Rp2s may be the same as or different from each other. In general formula (PA-1) and general formula (PA-3), Rp3 represents a single bond, —NH—, —CONH—, —CO ₂ —, —SO ₂ NH—, —O—, —S— or Represents SO ₂ —. * Represents a connecting part with B in the general formula (P).

In general formula (P), Rp1 is particularly preferably a methyl group or a phenyl group, and most preferably a methyl group. In general formula (PA-3), Rp2 is preferably a hydrogen atom or a halogen atom, and most preferably a hydrogen atom or a chlorine atom.

In the general formula (P), examples of the (t + 1) -valent linking group represented by B include an alkylene group, a cycloalkylene group, an arylene group, and a heteroarylene group. Among these, linking groups represented by the following structural formulas (PA-4) to (PA-9) are particularly preferable.

Among structural formulas (PA-4) to (PA-9), pigment derivatives having a linking group represented by the structural formula (PA-5) or (PA-8), particularly as B, are more excellent in dispersibility. This is preferable.

In general formula (P), examples of the alkylene group, cycloalkylene group and arylene group represented by D include methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene, cyclopentylene, Examples include cyclohexylene, cyclooctylene, cyclodecylene, phenylene, naphthylene, and the like. Among these, as D, an alkylene group is particularly preferable, and alkylene having 1 to 5 carbon atoms is most preferable.

In the general formula (P), when E represents —N (Rpa) (Rpb), examples of the alkyl group and aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, phenyl Group, naphthyl group and the like. As Rpa and Rpb, an alkyl group is particularly preferable, and an alkyl group having 1 to 5 carbon atoms is most preferable. T is preferably 1 or 2.

As specific examples of pigment derivatives, for example, the compounds of paragraphs 0217 to 0222 of JP2013-64998A can be referred to, and the contents thereof are incorporated in the present specification.

The content of the pigment derivative in the colored curable composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass with respect to the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

-solvent-
The solvent in the pigment dispersion is not particularly limited as long as it is an organic solvent used in general pigment dispersible compositions. A solvent may be used individually by 1 type and may be used together 2 or more types. For example, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol , 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, and the like, and a plurality of these may be used in combination to adjust the melting point, viscosity, and pigment dispersibility. Is also possible.

The content of the solvent in the pigment dispersion is appropriately selected according to the use of the pigment dispersion.
When the pigment dispersion is used for the preparation of a colored curable composition described later, from the viewpoint of handleability, the “total sum of the pigment and the pigment dispersant” is changed to “the total mass excluding the solvent of the pigment dispersion”. The content can be 5 to 50% by mass.

The content of the other colorant can be used within a range not impairing the effects of the present invention, and is preferably 10 to 55% by mass with respect to the total solid content of the colored curable composition of the present invention. More preferably, it is ˜45 mass%. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.

<Thermosetting compound>
The composition of the present invention contains at least one thermosetting compound. You may use a thermosetting compound and a photocurable compound together. Here, the thermosetting compound refers to a compound that can be cured by heating, and generally refers to a compound that is cured by heating at 180 ° C. or higher. Moreover, a photocurable compound means what can perform film | membrane hardening with light. In this invention, a thermosetting compound may be used independently and may be used in combination of 2 or more type.
As the thermosetting compound used in the present invention, for example, a compound having a thermosetting functional group can be used. Examples of the thermosetting functional group include those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, a (meth) acryloyl group, an isocyanate group, a vinyl group, and a mercapto group. preferable. As the thermosetting compound, those having two or more thermosetting functional groups in one molecule are more preferable, and compounds having two or more epoxy groups in one molecule are more preferable.
The thermosetting compound used in the present invention includes epoxy compounds, melamine compounds (for example, alkoxymethylated, acyloxymethylated melamine compounds), urea compounds (for example, alkoxymethylated, acyloxymethylated urea compounds), phenol compounds ( For example, preferred examples include hydroxymethylated or alkoxymethylated phenol compounds or resins, and alkoxymethyl etherified phenol compounds), epoxy compounds and melamine compounds are more preferred, and epoxy compounds are more preferred.

The thermosetting compound used in the present invention may be a low molecular compound (for example, a molecular weight of less than 2000, and further a molecular weight of less than 1000), or a high molecular compound (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). In the present invention, those having a molecular weight of 1000 or more are preferred, and those having a molecular weight of 2000 to 100,000 are more preferred. In the present invention, a compound having 2 or more epoxy groups in one molecule and a molecular weight of 1000 or more is particularly preferable.
The said weight average molecular weight can be calculated | required by the method similar to the weight average molecular weight of the halogenated phthalocyanine multimer mentioned above.

<Epoxy compound>
When the epoxy compound is a low molecular compound, a compound represented by the following general formula (EP1) can be mentioned.

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and has a substituent. May be. R ^EP1 and R ^EP2 and R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Examples of the substituent that the alkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfone group, an alkylsulfonyl group, and an alkylamino group. Groups, alkylamide groups, and the like.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 ~ R ^EP3 combines with Q ^EP may form a ring structure.
^nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.

When ^QEP is an ^nEP- valent organic group, ^QEP includes a chain or cyclic ^nEP- valent saturated hydrocarbon group (preferably having 2 to 20 carbon atoms), an ^nEP- valent aromatic ring group (carbon number). 6-30 are preferred), or a chain or cyclic saturated hydrocarbon or aromatic hydrocarbon, ether group, ester group, amide group, sulfonamide group, alkylene group (preferably having 1 to 4 carbon atoms, methylene group is A divalent linking group such as —N (—) ₂ , an n ^EP valent organic group having a structure in which a combination of these is connected, or the like is preferable.

As specific examples of the compound having an epoxy structure, for example, paragraph 0200 of JP2013-64998A can be referred to, and the contents thereof are incorporated in the present specification.

The epoxy compound used in the present invention is also preferably an oligomer or polymer having an epoxy group in the side chain. Examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins and the like.
These compounds may be commercially available or can be obtained by introducing an epoxy group into the side chain of the polymer.

As a commercial item, the following are mentioned, for example.
Examples of bisphenol A type epoxy resins include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 Etc.).
Examples of the bisphenol F type epoxy resin include JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (above, made by DIC Corporation), LCE-21, RE- 602S (Nippon Kayaku Co., Ltd.).
Phenol novolac type epoxy resins include JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation).
Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (above, Nippon Kayaku Co., Ltd.).
Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

In the case of synthesizing by introducing into a polymer side chain, for example, the introduction reaction includes tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, pyridine, The reaction can be carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using triphenylphosphine as a catalyst. The amount of the alicyclic epoxy unsaturated compound introduced is preferably controlled so that the acid value of the obtained polymer satisfies the range of 5 to 200 KOH · mg / g. The molecular weight is preferably in the range of 500 to 5000000, more preferably 1000 to 500000 on a weight average.
As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. Examples of such compounds include the following compounds.

The thermosetting compound used in the present invention is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of 100 ° C. or higher under normal pressure. (Meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate (for example, 3 to 6 functional (meth) acrylate) is preferable.
The following can be mentioned as the example.
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, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Ethylene with polyfunctional alcohols such as dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane (Meth) acrylated after adding oxide or propylene oxide,
Urethane (meth) acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490,
Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy polymers and (meth) acrylic acid,
And mixtures of these.
Among them, ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercially available product, NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipenta Erythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.

<Melamine compounds, urea compounds, other thermosetting compounds>
As the thermosetting compound used in the present invention, compounds having the following N-hydroxymethyl group, N-alkoxymethyl group, or N-acyloxymethyl group are also preferable. Such a compound is usually provided as a melamine compound or a urea compound.
As for these compounds, for example, paragraphs 0172 to 0194 of JP2013-066498A can be referred to, and the contents thereof are incorporated in the present specification.

The total content of the thermosetting compound in the composition of the present invention varies depending on the material, but is preferably 5 to 50% by mass, preferably 7 to 35% with respect to the total solid content (mass) of the colored curable composition. % By mass is more preferable, and 10 to 30% is particularly preferable. In this invention, the effect that the cured film excellent in chemical-resistance can be obtained by setting it as the compounding quantity of such a thermosetting compound is acquired.

<Solvent>
The colored curable composition of the present invention includes a solvent that dissolves at least a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, and a radical trapping agent. As this solvent, an organic solvent is usually used. A solvent may be used individually by 1 type and may be used together 2 or more types.
Examples of the organic solvent include the following.
Esters include 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 (examples) : Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (example: 3 -Methyl oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), 2-oxy Propionate alkyl ester (Eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, And ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.
Examples of ethers include 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 Examples include ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Aromatic hydrocarbons include toluene, xylene and the like.

These solvents are preferably mixed in two or more types from the viewpoint of improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the solvent in the colored curable composition is preferably such that the total solid content of the composition is 5 to 30% by mass, more preferably 7 to 25% by mass, from the viewpoint of applicability. 10 to 20% by mass is particularly preferable.

<Surfactant>
Various colored surfactants may be added to the colored curable 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. Only one type of surfactant may be used, or two or more types may be combined.

In particular, the colored curable composition of the present invention contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a colored curable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability 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 in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.
Examples of the fluorine-based surfactant include Megafac F781 (manufactured by DIC Corporation).
The colored curable composition may or may not contain a surfactant, but when it is contained, the addition amount of the surfactant is 0.001% by mass relative to the total mass of the colored curable composition. The content is preferably -2.0% by mass, more preferably 0.005% -1.0% by mass.

<Polymerization initiator>
The composition of the present invention may contain a polymerization initiator. Only one type of polymerization initiator may be used, or two or more types may be used. The content of the polymerization initiator in the composition of the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.1 to 15% by mass.
The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light or heat, or both, and can be appropriately selected according to the purpose. When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred. In addition, when the polymerization is initiated by heat, a polymerization initiator that decomposes at 150 to 250 ° C. is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group. For example, an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative Compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds, etc. Onium salt compounds, organoboron salt compounds, disulfone compounds, and the like.
From the viewpoint of sensitivity, oxime compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferred.

Specific examples of acetophenone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and oxime compounds include paragraphs 0506 to 0510 of JP2012-208494A (corresponding to US Patent Application Publication No. 2012/0235099). [0622-0628]) and the like can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the oxime compound include those represented by the following formula (OX-1) or (OX-2) in paragraph 0513 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/235099, [0632]). Reference can be made to the description of the compounds represented, the contents of which are incorporated herein.
As the oxime compound, commercially available products IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.
Also, commercial products such as TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) are used. it can. Commercial products such as Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA) can also be used.

<Various additives>
The colored curable composition of the present invention is various additives, for example, an acid anhydride, a curing agent, a curing catalyst, a filler, an adhesion promoter, and an antioxidant as long as the effects of the present invention are not impaired. An agent, an anti-aggregation agent and the like can be blended.

<Preparation method of colored curable composition>
A preferred method for preparing the colored curable composition of the present invention will be described. However, the present invention is not limited to this.
When the colorant is only a halogenated phthalocyanine dye, it is usually dissolved in the solvent together with the thermosetting compound and the radical trapping agent. Moreover, when it further contains a pigment as a coloring agent, it mix | blends after preparing as a pigment dispersion normally as above-mentioned.

In particular, when the thermosetting compound is an epoxy compound, a thermosetting compound and a curing catalyst or a curing agent are added to the pigment dispersion or dye solution thus obtained, or the binder is already thermosetting. In the case of a compound, it is preferable to prepare the colored curable composition in the present invention by adding a curing catalyst or a curing agent to impart a thermosetting function, and adding a solvent as necessary.

<Filter filtration>
The colored curable composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of the material of the filter include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore size of the filter within the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .

In the filter filtration, two or more filters may be used in combination.
For example, the filtration can be performed first using a first filter and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

<Application>
The colored curable composition of the present invention is cured and preferably used as a cured film. The layer obtained by curing the colored curable composition of the present invention can be preferably used as a colored layer of a color filter. In particular, it can be preferably used as a colored curable composition for dry etching.
In the present invention, the thickness of the colored layer is preferably from 0.1 to 1.0 μm, and more preferably from 0.1 to 0.8 μm.

<Color filter manufacturing method>
In the color filter of the present invention, at least one of the patterns constituting the color filter is a colored pattern formed from the above-described colored curable composition of the present invention. The color filter of the present invention is not particularly limited as long as at least one pattern is a colored pattern formed from the above-described colored curable composition of the present invention, but preferably the color of the present invention shown below. The filter is manufactured by a manufacturing method.

As an example of the method for producing the color filter of the present invention, a step of forming a colored layer using the colored curable composition of the present invention, a step of forming a photoresist layer on the colored layer, exposure and development Patterning the photoresist layer to obtain a resist pattern, and dry etching the colored layer using the resist pattern as an etching mask.

In the method for producing a color filter of the present invention, the first colored layer is formed using the above-described colored curable composition of the present invention (also referred to as the first colored curable composition).
Here, since the 1st colored layer is formed with the colored curable composition of this invention, it is excellent in solvent resistance and alkali developing solution resistance.
As a result, a developer used when forming a resist pattern (patterned photoresist layer) as an etching mask on the first colored layer, which will be described in detail later, or a second on the first colored layer. In the step of forming the second colored radiation-sensitive layer with the colored radiation-sensitive composition and the step of forming the third colored radiation-sensitive layer with the third colored radiation-sensitive composition on the first colored layer, The first colored layer exposes the organic solvent in the second or third colored radiation-sensitive composition or the second or third colored radiation-sensitive layer formed by the second or third colored radiation-sensitive composition; When dissolved in the developer used for development, the color component in the first colored layer may be eluted into the solvent or developer, or the color component in the second or third colored radiation-sensitive composition is Mixed in the first colored layer Fear, etc. can be suppressed. As a result, it is possible to suppress the occurrence of color fading in the first colored layer and the occurrence of overlapping regions in which a plurality of colors overlap each other, so that the performance of the finally obtained color filter can be improved.
In particular, for a solid-state imaging device that requires a minute size such that the thickness is 0.1 to 1.0 μm and / or the pixel pattern size (one side in a square pattern) is 2 μm or less (for example, 0.5 to 2.0 μm). It is effective for producing a color filter.

Here, the solid-state imaging device will be briefly described with reference to FIG. 4 as an example.
As shown in FIG. 4, the solid-state imaging device 10 includes a light receiving element (photodiode) 42 provided on a silicon substrate, a color filter 13, a planarizing film 14, a microlens 15, and the like. In the present invention, the planarizing film 14 is not necessarily provided. In FIG. 4, in order to clarify each part, the ratios of the thicknesses and widths are ignored, and some parts are exaggerated.

The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter 13 as long as the present invention is not impaired.

A P well 41 is provided on the silicon substrate, and a photodiode 42 is provided on a part of the surface of the P well 41. The photodiode 42 is formed by performing heat treatment after ion-implanting N-type impurities such as P and As into a part of the surface of the P well 41. In addition, an impurity diffusion layer 43 having an N-type impurity concentration higher than that of the photodiode 42 is provided in a region different from the above portion on the surface of the P well 41 of the silicon substrate. The impurity diffusion layer 43 is formed by performing heat treatment after ion implantation of N-type impurities such as P and As. The impurity diffusion layer 43 serves as a floating diffusion layer that transfers charges generated when the photodiode 42 receives incident light. In addition to the P-well 41 being a P-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 being an N-type impurity layer, the P-well 41 is an N-type impurity layer, and the photodiode 42 and the impurity diffusion layer 43 are being P-type impurity layers. Can also be implemented.

An insulating film 47 such as SiO ₂ or SiO ₂ / SiN / SiO ₂ is provided on the P well 41, the photodiode 42, and the impurity diffusion layer 43. On the insulating film 47, poly-Si, tungsten, An electrode 44 made of tungsten silicide, Al, Cu or the like is provided. The electrode 44 serves as the gate of the gate MOS transistor, and can serve as a transfer gate for transferring charges generated in the photodiode 42 to the impurity diffusion layer 43. Further, a wiring layer 45 is formed above the electrode 44. Above the wiring layer 45, a BPSG film 46 and a P-SiN film 48 are provided. The interface between the BPSG film 46 and the P-SiN film 48 is formed so as to be curved downward above the photodiode 42, and serves as an in-layer lens for efficiently guiding incident light to the photodiode 42. Fulfill. On the BPSG film 46, a planarizing film layer 49 is formed for the purpose of planarizing the surface of the P-SiN film 48 or uneven portions other than the pixel region.

The color filter 13 is formed on the planarizing film layer 49. In the following description, a colored film (so-called solid film) formed on a silicon substrate without dividing the region is referred to as a “colored (colored radiation sensitive) layer”, and is formed by dividing the region into a pattern. A colored film (for example, a film patterned in a stripe shape) is referred to as a “colored pattern”. In addition, among the colored patterns, a colored pattern that is an element constituting the color filter 13 (for example, a colored pattern patterned into a square or a rectangle) is referred to as a “colored (red, green, blue) pixel”.

The color filter 13 includes a plurality of two-dimensionally arranged green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B. Each of the

colored pixels

20R, 20G, and 20B is formed above the light receiving element 42. The green pixels 20G are formed in a checkered pattern, and the blue pixels 20B and the red pixels 20R are formed between the green pixels 20G. In FIG. 4, in order to explain that the color filter 13 is composed of pixels of three colors, the

colored pixels

20R, 20G, and 20B are displayed in a line.

The planarization film 14 is formed so as to cover the upper surface of the color filter 13 and planarizes the color filter surface.

The microlens 15 is a condensing lens arranged with the convex surface facing upward, and is provided above the planarizing film 14 (or a color filter when the planarizing film 14 is not provided) and above the light receiving element 42. . Each microlens 15 efficiently guides light from the subject to each light receiving element 42.

Next, the manufacturing method of the color filter which concerns on embodiment of this invention is demonstrated.
In the method for producing a color filter according to the embodiment of the present invention, first, as shown in the schematic cross-sectional view of FIG. Form (step (I)). Here, the first colored curable composition is the colored curable composition of the present invention.

The first colored layer 11 can be formed by applying a colored curable composition on a support by a coating method such as spin coating, slit coating or spray coating, and drying to form a colored layer.

Here, the thickness of the first colored layer 11 is preferably in the range of 0.3 to 1.0 μm, more preferably in the range of 0.35 to 0.8 μm, and more preferably in the range of 0.35 to 0.7 μm. .

The first colored curable composition contains a thermosetting compound. For this reason, it is preferable that the first colored layer 11 is heated and cured by a heating device such as a hot plate or an oven. The heating temperature is preferably 120 ° C. to 250 ° C., and more preferably 160 ° C. to 230 ° C. The heating time varies depending on the heating means, but is usually about 3 to 30 minutes when heated on a hot plate, and usually about 30 to 90 minutes when heated in an oven.

Next, patterning is performed by dry etching so that a through hole group is formed in the first colored layer 11 (step (II)). Thereby, a first colored pattern is formed. According to this method, after forming the first colored layer with the colored radiation-sensitive composition, the first colored layer is exposed and developed to form a through hole having a desired shape as compared with the case where the through hole group is provided. A hole group can be provided more reliably. This is because, in a colored radiation-sensitive composition in which the content of the colorant with respect to the total solid content of the composition is 50% by mass or more, there is limited room for adding a component that contributes to developability to the composition. This is because reliable patterning becomes difficult.

The first colored pattern may be a colored pattern provided as the first color on the support, or may be a colored pattern provided as a pattern for the second color or the third color or later on the support having an existing pattern in some cases. .

Dry etching can be performed on the first colored layer 11 using an etching gas with the patterned photoresist layer as a mask. For example, as shown in the schematic cross-sectional view of FIG. 3 of Japanese Patent Application Laid-Open No. 2013-64998, first, a photoresist layer 51 is formed on the first colored layer 11.

Specifically, a positive or negative radiation-sensitive composition is applied (preferably applied) on the colored layer and dried to form a photoresist layer. In forming the photoresist layer 51, 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. As this positive type radiation sensitive composition, positive type photo 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.

The thickness of the photoresist layer 51 is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm. The application of the photoresist layer 51 can be suitably performed using the application method for the first colored layer 11 described above.

Next, as shown in the schematic cross-sectional view of FIG. 4 of JP2013-64998A, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photo resist) provided with a resist through-hole group 51A. Resist layer) 52 is formed.
The formation of the resist pattern 52 is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing the resist through hole group 51 </ b> A in the photoresist layer 51 by exposure and development, a resist pattern 52 as an etching mask used in the next etching is provided on the first colored layer 11.

The exposure of the photoresist layer 51 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. be able to. 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 first colored layer containing the colorant. A combination of these organic solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 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, as shown in the schematic cross-sectional view of FIG. 5 of JP 2013-64998 A, patterning is performed by dry etching so that the through hole group 120 is formed in the first colored layer 11 using the resist pattern 52 as an etching mask. To do. Thereby, the 1st coloring pattern 12 is formed. Here, the through-hole group 120 has a first through-hole part group 121 and a second through-hole part group 122.
The through-hole group 120 is provided in a checkered pattern in the first colored layer 11. Therefore, the 1st coloring pattern 12 by which the through-hole group 120 is provided in the 1st coloring layer 11 has a some square-shaped 1st coloring pixel in checkered form.

Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 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, and the like. There is a method described in this publication.

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 refers to the remaining film thickness of the film to be etched.

Further, the 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 preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

Next, as shown in the schematic cross-sectional view of FIG. 6 of JP2013-64998A, the resist pattern (that is, etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 includes a step of applying a stripping solution or a solvent to the resist pattern 52 so that the resist pattern 52 can be removed, and a step of removing the resist pattern 52 using cleaning water. Is preferred.

As a step of applying a stripping solution or solvent on the resist pattern 52 to make the resist pattern 52 removable, for example, a stripping solution or solvent is applied on at least the resist pattern 52, and the paddle is stagnated for a predetermined time. A step of developing 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 step of removing the resist pattern 52 using cleaning water include a step of removing the resist pattern 52 by spraying cleaning water onto the resist pattern 52 from a spray type or shower type spray nozzle. it can. 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 52 is more effectively moved by spraying the cleaning water by moving from the support center to the support end twice or more during the step of removing the resist pattern 52. Can be removed.

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. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine. Preferably, they are monoethanolamine, diethanolamine, and triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of cyclic nitrogen-containing compounds 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, and 2,6-lutidine. 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 includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes 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.

Next, as shown in the schematic cross-sectional view of FIG. 7 of JP2013-64998A, the second colored radiation-sensitive composition is formed inside each through-hole in the first through-hole portion group 121 and the second through-hole portion group 122. The first colored layer (that is, the first colored pattern 12 in which the through-hole group 120 is formed in the first colored layer 11) is formed on the first colored layer so that a plurality of second colored pixels are formed by embedding the object. The 2nd colored radiation sensitive layer 21 is laminated | stacked with a 2 colored radiation sensitive composition (process (c)). Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the through-hole group 120 of the 1st coloring layer 11 is formed. Here, the second colored pixel is a square pixel. The second colored radiation sensitive layer 21 can be formed in the same manner as the method for forming the first colored layer 11 described above.
The thickness of the second colored radiation-sensitive layer 21 here is preferably in the range of 0.3 to 1 μm, more preferably in the range of 0.35 to 0.8, and more preferably in the range of 0.35 to 0.7 μm. preferable.

Then, the second colored radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first through-hole portion group 121 provided in the first colored layer 11 of the second colored radiation-sensitive layer 21. And the plurality of second colored pixels 22R provided inside each through hole of the second through hole portion group 122 (step (d)) (schematic cross section of FIG. 8 of Japanese Patent Laid-Open No. 2013-64998) (See diagram).

Next, as shown in the schematic cross-sectional view of FIG. 9 of JP2013-64998A, a third colored radiation-sensitive composition is embedded in each through-hole in the second through-hole portion group 122 to obtain a plurality of The third color sensation is formed on the first color layer (that is, the first color pattern 12 in which the second color pattern 22 is formed in the first through-hole portion group 121) so that the third color pixel is formed. The 3rd colored radiation sensitive layer 31 is formed with a radiation composition (process (e)). Thereby, the third colored pattern 32 having a plurality of third colored pixels is formed in the second through-hole portion group 122 of the first colored layer 11. Here, the third colored pixel is a square pixel. The third colored radiation-sensitive layer 31 can be formed in the same manner as the method for forming the first colored layer 11 described above.
The thickness of the third colored radiation-sensitive layer 31 here is preferably in the range of 0.3 to 1 μm, more preferably in the range of 0.35 to 0.8, and more preferably in the range of 0.35 to 0.7 μm. preferable.

Then, the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second through-hole portion group 122 provided in the first colored layer 11 of the third colored radiation-sensitive layer 31. As shown in the schematic cross-sectional view of FIG. 10 of JP2013-64998A, the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is removed. Is manufactured (step (f)).

The second colored radiation-sensitive composition and the third colored radiation-sensitive composition described above each contain a colorant. Examples of the colorant include those described above for the colored curable composition of the present invention, but one of the second colored pixel and the third colored pixel is a red transmissive portion, and the other is a blue transmissive portion. Are preferably a red transmissive part or a blue transmissive part, respectively. The colorant contained in the colored curable composition for forming the red transmission part is C.I. I.

Pigment Orange

2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, And C.I. I.

Pigment Red

1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 seed Is preferably above, the colorant contained in the colored curable composition for forming a blue transmission unit, C. I.

Pigment Violet

1, 19, 23, 27, 32, 37, 42, and C.I. I.

Pigment Blue

1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 or more It is preferable.

In each of the second colored radiation-sensitive composition and the third colored radiation-sensitive composition, the content of the colorant composition with respect to the total solid content is preferably 30% by mass or more, and 35% by mass. More preferably, it is more preferably 40% by mass or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.

Also, it is preferable that a negative radiation sensitive composition is used for each of the second colored radiation sensitive composition and the third colored radiation sensitive composition. As this negative type radiation sensitive composition, there is a negative type feeling 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 radiation composition can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.

Specifically, the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin or the like), and the like. Examples described in paragraph Nos. [0017] to [0064] of JP-A-2005-326453. Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.

The exposure with respect to the 2nd colored radiation sensitive layer 21 and the 3rd colored radiation sensitive layer 31 can be performed by exposing with g line | wire, h line | wire, i line | wire, etc., Preferably i line | wire.
The development performed after exposure is usually performed by developing with a developer.
Examples of the developer include the same developers as those already described in the exposure and development of the photoresist layer 51.
When an alkaline aqueous solution is used as a developer, a washing treatment with water is generally performed after development.

The length of one side of the first colored pixel, the second colored pixel, and the third colored pixel (the length of the short side when the pixel is a rectangle, and the length of one side when the pixel is a square) is From the viewpoint of image resolution, 0.5 to 1.7 μm is preferable, and 0.6 to 1.5 μm is more preferable.

According to the method for producing a color filter of the present invention described above, the first colored layer, and thus the first colored pixel, is formed of the colored curable composition having a high concentration of the colorant of the present invention. The thickness of one colored pixel can be extremely reduced (for example, 0.7 μm or less). Thereby, it can be set as the manufacturing method of the color filter which can manufacture the color filter by which crosstalk (color mixture of light) was suppressed.
Moreover, as described above, the first colored pixel formed by the colored curable composition of the present invention has excellent solvent resistance and alkali developer resistance. Thereby, generation | occurrence | production of the overlap area | region which overlaps with the color in another coloring layer and another coloring pattern can be reduced, As a result, a high performance color filter can be manufactured.

The color filter obtained from the colored curable composition of the present invention can be suitably used for a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.). Moreover, it can use suitably also for image display devices, such as electronic paper and organic EL. In particular, the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD and a CMOS.

The color filter of the present invention is also suitable as a color filter for a liquid crystal display device. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color tone and excellent display characteristics.

For the definition of the display device and details of each display device, for example, the description of paragraph numbers 0395 to 0398 in JP 2013-64998 A can be referred to, and the contents thereof are incorporated in the present specification.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.

<Halogenated phthalocyanine dye>
Halogenated phthalocyanine dye A: In the following structures, a to c each represent the number of partial structures represented in parentheses, and a = 12, b = 2, and c = 2.

Halogenated phthalocyanine dye B: In the following structures, a and b represent the number of partial structures represented in parentheses, respectively, and represent a = 12, b = 4.

Halogenated phthalocyanine dye C: In the following structures, a to c each represent the number of partial structures represented in parentheses, and a = 12, b = 2, and c = 2.

Halogenated phthalocyanine dye D: In the following structure, a and b represent the number of partial structures represented in parentheses, respectively, and represent a = 12, b = 4.

Halogenated phthalocyanine dye E: In the following structures, a and b represent the number of partial structures represented in parentheses, respectively, and a = 12 and b = 4.

Halogenated phthalocyanine dye F (multimer of halogenated phthalocyanine dye E)
<Non-halogenated phthalocyanine dye>
Non-halogenated phthalocyanine dye A: In the following structures, a and b each represent the number of partial structures represented in parentheses and satisfy a + b = 16.

<Halogenated phthalocyanine pigment>
Halogenated phthalocyanine pigment A: P.I. G58 (Pigment Green 58)

<< Synthesis Example 1 Synthesis of Halogenated Phthalocyanine Dye A >>
Tetrachlorophthalonitrile (80.0 g, 300.9 mmol), the following compound 1 (59.03 g, 300.9 mmol) and 400.0 g of acetonitrile were added to the flask. After stirring for 30 minutes until the internal temperature of the flask was stabilized at 40 ° C., potassium carbonate (45.74 g, 330.9 mmol) was added and allowed to react for about 3 hours. After cooling, the solution obtained by suction filtration was concentrated under reduced pressure at 40 ° C. for 1 hour, the solvent was distilled off, and then vacuum dried at 110 ° C. overnight to obtain about 128 g (99.9%) of Compound A. .
A flask was charged with compound A (125.0 g, 293.7 mmol) and 146.83 mL of benzonitrile, and stirred for about 1 hour under a nitrogen stream (10 mL / min) until the internal temperature of the flask was stabilized at 150 ° C. did. Thereafter, 26.81 g (84.0 mmol) of zinc iodide was added thereto and reacted for about 48 hours. After cooling, 2000 mL of methanol was added thereto and crystallized by stirring at room temperature. The precipitated solid was taken out by decantation, 2000 mL of methanol was added to the obtained solid, and the mixture was heated and stirred at 60 ° C. for 1 hour. After cooling this, suction filtration was performed, and the resulting crystals were blown and dried overnight at 40 ° C. to obtain about 104.5 g (80.5%) of Compound B. This compound B corresponds to the halogenated phthalocyanine dye E described above.
Compound B (30.0 g, 16.97 mmol), THF / water (1: 1) 300 mL, and lithium hydroxide (0.81 g, 33.94 mmol) were charged into the flask, and the internal temperature of the flask was adjusted to 60 ° C. Stir for about 7 hours. After cooling this, 102 mL of 1M hydrochloric acid was added thereto and stirred at room temperature for 30 minutes. The solution was concentrated under reduced pressure at 40 ° C. for 1 hour, and the solvent was distilled off. Subsequently, 50 mL of methanol was added to the obtained residue and suction filtered, and the obtained crystal was blown and dried overnight at 40 ° C. to obtain about 1.54 g (88.2%) of a halogenated phthalocyanine dye A.
Compound 1

Synthesis Example 2 Synthesis of Halogenated Phthalocyanine Dye F
The above compound B (halogenated phthalocyanine dye E) (1.75 g, 1.06 mmol), DMF 20 mL, 1 M aqueous sodium hydroxide solution 1.06 mL was added to the flask, and the mixture was stirred at an internal temperature of 60 ° C. for about 6 hours. After cooling, 10 mL of 1M hydrochloric acid was added. 50 mL of methanol was added to this solution and suction filtered, and the resulting solid was blown and dried overnight at 40 ° C. to obtain about 1.48 g of Compound C.
Compound C (1.5 g), 0.18 g of glycidyl methacrylate, 0.23 g of tetrabutylammonium bromide, 0.02 g of p-methoxyphenol, and 9.0 mL of propylene glycol monomethyl ether were added to the flask and stirred at 100 ° C. for about 8 hours. did. To this reaction liquid, 45 mL of methanol was added and suction filtered, and the resulting crystal was blown and dried overnight at 40 ° C. to obtain about 1.21 g of Compound D.
Compound D

In a three-necked flask, compound D (24.2 g), methacrylic acid (1.08 g), dodecyl mercaptan (0.25 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, Compound D (24.2 g), methacrylic acid (1.08 g), dodecyl mercaptan (0.25 g), 2,2′-azobis (isobutyric acid) dimethyl (0.58 g) [trade name: V601, Wako Pure Chemical Industries, Ltd.] and PGMEA (23.3 g) were added dropwise over 2 hours. Then, after stirring for 3 hours, the temperature was raised to 90 ° C., the mixture was heated and stirred for 2 hours, and then allowed to cool to obtain a PGMEA solution of a multimeric intermediate. Next, glycidyl methacrylate (1.42 g), tetrabutylammonium bromide (80 mg), and p-methoxyphenol (20 mg) are added and heated in an air atmosphere at 100 ° C. for 15 hours to eliminate glycidyl methacrylate. Confirmed. After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL for reprecipitation to obtain 47.6 g of a halogenated phthalocyanine dye F.
The weight average molecular weight (Mw) of the halogenated phthalocyanine dye F confirmed by GPC measurement was 6,500, and the ratio of the weight average molecular weight / number average molecular weight (Mw / Mn) was 1.9.

<< Synthesis Example 2 Synthesis of Phthalocyanine Dye BE and Non-Halogenated Phthalocyanine Dye >>
In Synthesis Example 1, other phthalocyanine dyes were synthesized by appropriately changing the raw materials.

<Other colorants>
Azo dye (pigment) A: P.I. Y150

<Derivative>
Derivative A: the following compound

<Dispersant>
Dispersant A: the following compound (synthesized with reference to paragraph number 0334 of JP-A-2007-277514)

In the above, a is 2.0, b is 4.0, acid value is 10 mgKOH / g, and Mw20000.
Further, a and b in the dispersant A each represent the number of partial structures represented in parentheses and satisfy a + b = 6.
Dispersant B: Disperbyk-107 manufactured by BYK Chemie

<Radical trapping agent>
Naphthalene derivative A: manufactured by Tokyo Chemical Industry Co., Ltd. 1,4-dihydroxynaphthalene thioether compound A: manufactured by Tokyo Chemical Industry Co., Ltd. 3,3′-thiodipropionic acid dimethyl hindered amine compound A: manufactured by BASF TINUVIN123
Hindered amine compound B: Adekastab LA-52 manufactured by ADEKA Corporation
Ultraviolet absorber A: TINUVIN900 manufactured by BASF
Ultraviolet absorber B: TINUVIN234
Thermal polymerization inhibitor A: p-methoxyphenol thermal polymerization inhibitor B: ADEKA Corporation Adeka Stub AO-60

<Thermosetting compound>
Epoxy compound A: EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., molecular weight = 2234) Epoxy compound B: glycidyl trityl ether, manufactured by Tokyo Chemical Industry Co., Ltd.

<Surfactant>
Surfactant A: Megafac F781 (manufactured by DIC Corporation, fluorine type surfactant)

<Preparation of pigment dispersion>
The mixed solution containing the following compound was mixed for 3 hours with a bead mill (high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism) using zirconia beads having a diameter of 0.3 mm. Dispersed to prepare a pigment dispersion. The types of pigments are those listed in Table 5 below.
-Pigment P.I. Y150 or P.I. G58: 15 parts by mass Derivative A: 0.5 parts by mass Dispersant A or B: 7.0 parts by mass Solvent: PGMEA: 90 parts by mass

<Preparation of colored curable composition>
Each of the following components (compounds described in the following table for details) were mixed and stirred to prepare a colored curable composition. In Table 5 below, “-” indicates that no blending was performed.
<< Example 1 >>
-Halogenated phthalocyanine dye: 60 parts by mass in 100 parts by mass of total solids-Radical trapping agent: 5 parts by mass in solids-Thermosetting compound: 34 parts by mass in 100 parts by mass of total solids-Surfactant: Total solids 1 part by mass per 100 parts by mass. Solvent: amount that results in a final solid content concentration of 15% by mass << Examples 2 to 10 >>
Halogenated phthalocyanine dye: 45 parts by mass in 100 parts by mass of total solids Pigment dispersion (prepared above): 22.5 parts by mass in 100 parts by mass of total solids Radical trapping agent: 100 parts by mass of total solids 5 parts by mass in the part, thermosetting compound: 26.5 parts by mass in 100 parts by mass of the total solid, surfactant: 1 part by mass in 100 parts by mass of the total solid, and solvent: 15% by mass of the final solid content concentration. Amount << Example 11 >>
-Halogenated phthalocyanine dye: 70 parts by mass in 100 parts by mass of total solids-Radical trapping agent: 5 parts by mass in 100 parts by mass of total solids-Thermosetting compound: 24 parts by mass in 100 parts by mass of total solids-Surface activity Agent: 1 part by mass in 100 parts by mass of the total solid content. Solvent: Amount at which the final solid content concentration becomes 15 mass% << Examples 12 to 20, 22 to 26, Comparative Example 5 >>
-Halogenated phthalocyanine dye: 50 parts by mass in 100 parts by mass of total solids-Pigment dispersion (prepared above): 30 parts by mass in 100 parts by mass of total solids-Radical trapping agent: in 100 parts by mass of total solids 5 parts by mass / thermosetting compound: 14 parts by mass in 100 parts by mass of total solids / surfactant: 1 part by mass in 100 parts by mass of total solids / solvent: an amount in which the final solid content concentration is 15% by mass << Example 21 >>
-Halogenated phthalocyanine dye: 30 parts by mass in 100 parts by mass of total solids-Pigment dispersion (prepared above): 15 parts by mass in 100 parts by mass of total solids-Radical trapping agent: in 100 parts by mass of total solids 5 parts by mass-thermosetting compound: 49 parts by mass in 100 parts by mass of total solid-Surfactant: 1 part by mass in 100 parts by mass of total solid-Solvent: an amount in which the final solid content concentration is 15% by mass << Example 27 >>
A colored curable composition of Example 27 was prepared in the same manner as in Example 4, except that the halogenated phthalocyanine dye A was changed to the halogenated phthalocyanine dye F.
<< Comparative Example 1 >>
-Halogenated phthalocyanine dye: 45 parts by mass in 100 parts by mass of total solids-Pigment dispersion (prepared above): 22.5 parts by mass in 100 parts by mass of total solids-Thermosetting compound: 100 in total solids 31.5 parts by weight in parts by weight, surfactant: 1 part by weight in 100 parts by weight of total solids, solvent: an amount that results in a final solids concentration of 15% by weight << Comparative Example 2 >>
・ P. Pigment dispersion using G58 (prepared above): 67.5 parts by mass / P. Pigment dispersion using Y150 (prepared above): 22.5 parts by mass in 100 parts by mass of total solids, thermosetting compound: 9 parts by mass in 100 parts by mass of total solids, surfactant: all solids 1 part by mass in 100 parts by mass / solvent: An amount that results in a final solid content concentration of 15% by mass << Comparative Example 3 >>
・ P. Pigment dispersion using G58 (prepared above): 67.5 parts by mass / P. Pigment dispersion using Y150 (prepared above): 2 in 100 parts by weight of total solids
2.5 parts by mass-radical trapping agent: 5 parts by mass in 100 parts by mass of total solids-thermosetting compound: 4 parts by mass in 100 parts by mass of total solids-surfactant: 1 part by mass in 100 parts by mass of total solids Parts / solvent: an amount at which the final solid content concentration becomes 15% by mass << Comparative Example 4 >>
Halogenated phthalocyanine dye: 50 parts by mass in 100 parts by mass of total solids Pigment dispersion (prepared above): 30 parts by mass in 100 parts by mass of total solids Thermosetting compound: 100 parts by mass of total solids 19 parts by mass / surfactant: 1 part by mass of 100 parts by mass of total solids / solvent: the amount at which the final solid content concentration is 15% by mass

The following evaluation was performed about the obtained composition.

<Method for evaluating the number of foreign object defects>
The composition obtained above was applied onto a 7.5 cm × 7.5 cm glass substrate using a spin coater so as to form a coating film having a thickness of 0.6 μm. And dried for 2 minutes (pre-baked) to form a colored film (colored layer).
Foreign matter contained in the colored film (colored film after exposure and development after pre-baking) was detected with a foreign substance evaluation apparatus Conplus III (manufactured by Applied Materials). From all the detected foreign matters, foreign matters having a maximum width of 1.0 μm or more that cause a decrease in yield were visually classified. The number of classified foreign matters having a maximum width of 1.0 μm or more (number per 1 cm ² ) was counted, and film defects were evaluated using the obtained value as an index.
Note that the foreign substance evaluation apparatus Conplus III has a different number of foreign substances depending on the state of the film. Therefore, it is necessary to confirm the in-plane uniformity of the film thickness in advance when evaluating the foreign substance. For the group of coating films having in-plane uniformity within 100 nm, the number of foreign matters can be compared in the same row. In-plane uniformity means the film thickness difference between the maximum film thickness and the minimum film thickness (maximum film thickness-minimum film thickness) within the 8-inch wafer surface of the coating film.

As apparent from Table 5 above, a colored layer formed using a colored curable composition containing a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, a radical trapping agent, and a solvent for dissolving them (Example 1) From (27) to (27), it was found that the number of foreign matter defects was small as compared with the case without this configuration.
In contrast, when the colored curable composition does not contain a radical trapping agent (Comparative Examples 1 and 4), the colored curable composition contains no radical trapping agent and is not a halogenated phthalocyanine dye but a phthalocyanine. When a pigment is used (Comparative Example 2), when a phthalocyanine pigment is used instead of a halogenated phthalocyanine dye (Comparative Example 3), when the phthalocyanine dye does not contain a halogen (Comparative Example 5), foreign matter defects in the formed colored layer It turned out that there are many numbers compared with an Example.

1 Fine foreign matter 2 Halogenated phthalocyanine dye,
3 Radical trapping agent 4 Halogenated phthalocyanine pigment 13 Color filter 14 Flattening film 15 Microlens 20G Green pixel (first color pixel)
20R red pixel (second color pixel)
20B Blue pixel (third color pixel)
41 P well 42 Light receiving element (photodiode)
43 Impurity diffusion layer 44 Electrode 45 Wiring layer 46 BPSG film 47 Insulating film 48 P-SiN film 49 Flattening film layer

Claims

A colored curable composition comprising a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, a radical trapping agent, and a solvent for dissolving them.
The colored curable composition according to claim 1, wherein the radical trapping agent contains at least one compound containing at least one ring structure.
The colored curable composition according to claim 1 or 2, wherein the radical trapping agent contains at least one selected from a hindered amine compound, an ultraviolet absorber, and a thermal polymerization inhibitor.
The colored curable composition according to any one of claims 1 to 3, wherein the halogenated phthalocyanine dye is represented by the following general formula (1);

In the general formula (1), Z 1 to Z 16 are each a hydrogen atom or a substituent,
At least one of the substituents is a halogen atom;
At least one other substituent is an aromatic group, a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), or a group represented by the following formula (2A). A group containing at least one functional group selected from a group to be selected, an amino group and a thiol group;
M represents two hydrogen atoms, metal atoms, metal oxides or metal halides;

In formula (1A), R 1 represents an alkyl group having a fluorine atom;

In formula (2A), R 2 and R 3 are each independently an alkyl group, and R 2 and R 3 may be bonded to each other to form a ring.
In the general formula (1), 1 to 8 of Z 1 to Z 16 are
A group represented by the following general formula (1-2);
A group represented by the general formula (1-4), a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), and a group represented by the following formula (2A). A group containing at least one functional group selected from a group, an amino group, and a thiol group,
The colored curable composition according to claim 4, which represents at least one selected from the group consisting of:

In general formula (1-2), X is an oxygen atom or a sulfur atom, and A 1 is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. ; General formula (1-4)

In general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4.

In formula (1A), R 1 represents an alkyl group having a fluorine atom;

In formula (2A), R 2 and R 3 are each independently an alkyl group, and R 2 and R 3 may be bonded to each other to form a ring.
In the general formula (1), 1 to 8 of Z 1 to Z 16 are
It represents a group represented by the following general formula (1-2) or a group represented by the following general formula (1-4), and at least one is a group represented by the general formula (1-2) Or
A group represented by the following general formula (1-2), a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), and a group represented by the following formula (2A) Represents a group containing at least one functional group selected from the group consisting of amino group and thiol group,
The colored curable composition according to claim 4 or 5; the general formula (1-2)

In general formula (1-2), X is an oxygen atom or a sulfur atom, and A 1 is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. ; General formula (1-4)

In general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4;

In formula (1A), R 1 represents an alkyl group having a fluorine atom;

In formula (2A), R 2 and R 3 are each independently an alkyl group, and R 2 and R 3 may be bonded to each other to form a ring.
The colored curable composition according to any one of claims 1 to 3, wherein the halogenated phthalocyanine dye is represented by the following general formula (1-1);

In the general formula (1-1), Z 1 to Z 16 are each a hydrogen atom, a halogen atom, a group represented by the following general formula (1-1-2), or a group represented by the following general formula (1-3). Or a group represented by the following general formula (1-4),
1 to 8 of Z 1 to Z 16 represent a group represented by the following general formula (1-1-2) or a group represented by the following general formula (1-4),
At least one is a halogen atom, and at least one is a group represented by the following general formula (1-1-2);
M represents two hydrogen atoms, a metal atom, a metal oxide or a metal halide; general formula (1-1-2)

In general formula (1-1-2), X 1 is an oxygen atom or a sulfur atom, and A 11 is a phenyl group having 1 to 5 substituents R, or a naphthyl group having 1 to 7 substituents R. And the substituent R is represented by any one of the following general formulas (4) to (6): a nitro group, COOR 1 , OR 2 , a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms. Or a group selected from the following general formula (X); R 1 is a group represented by the following general formula (1-3) or an alkyl group having 1 to 8 carbon atoms; R 2 Is an alkyl group having 1 to 8 carbon atoms;

In general formula (4), R 4 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents an optionally substituted diarylamino group, or an optionally substituted alkylarylamino group;
In the general formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R 5 is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, R 5 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. A diarylamino group which may have a substituent, a substituent or an alkylarylamino group which may have a substituent;
In general formula (6), R 6 and R 7 are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, An arylcarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent;

In general formula (X), R 11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
n1 represents an integer of 1 to 3; when n1 is 2 or 3, the plurality of R 11 may be the same or different;
Y 1 represents —O—, —S—, —NR 13 —, —SO 2 —, or —C (═O) —. R 13 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R 12 represents a monovalent substituent.
General formula (1-3)

In the general formula (1-3), R 3 represents an alkylene group having 1 to 3 carbon atoms, R 4 represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4; 1-4)

In general formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4.
1 to 4 of Z 1 to Z 16 are represented by a carboxyl group, an epoxy group, an aryl ester group, a tertiary alkyl ester group, a group represented by the following formula (1A), or a formula (2A) The colored curable composition according to any one of claims 4 to 7, which has at least one functional group selected from a group, an amino group, and a thiol group;

In formula (1A), R 1 represents an alkyl group having a fluorine atom;

In formula (2A), R 2 and R 3 are each independently an alkyl group, and R 2 and R 3 may be bonded to each other to form a ring.
The colored curable composition according to any one of claims 1 to 8, wherein the colorant further contains a yellow pigment.
The colored curable composition according to any one of claims 1 to 9, wherein the thermosetting compound has two or more epoxy groups in one molecule.
The colored curable composition according to any one of claims 1 to 10, wherein the total content of the colorant is 60 to 90% by mass with respect to the total solid content of the colored curable composition.
The colored curable composition according to any one of claims 1 to 11, wherein the halogenated phthalocyanine dye is a multimer.
A cured film obtained by curing the colored curable composition according to any one of claims 1 to 12.
A color filter having a colored layer using the colored curable composition according to any one of claims 1 to 12.
The color filter according to claim 14, wherein the colored layer has a thickness of 0.1 to 0.8 µm.
A step of curing a colored curable composition containing a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, a radical trapping agent, and a solvent for dissolving them, to form a colored layer;
Forming a photoresist layer on the colored layer;
Patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry etching the colored layer using the resist pattern as an etching mask;
A method for producing a color filter, comprising:
A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to claim 14 or 15.
A liquid crystal display device, an organic electroluminescence element, or a solid-state image sensor having a color filter manufactured by the method for manufacturing a color filter according to claim 16.