JP2012158740A - Dye compound, method for producing dipyrromethene metal complex compound, method for producing dye multimer, and substituted pyrrole compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye compound excellent in heat resistance and good in color purity.SOLUTION: The dye compound has a partial structure represented by formula (5) (wherein Dye denotes a dye structure; Gdenotes NR or oxygen; Gdenotes a monovalent substituent having a steric parameter, -Es' value, of ≥1.5; p denotes an integer of 1 to 8, and when p is ≥2, the structures in the parentheses may be the same or different; and R denotes hydrogen or a monovalent substituent).

Description

  The present invention relates to a dye compound, a method for producing a dipyrromethene metal complex compound, a method for producing a dye multimer, and a substituted pyrrole compound.

In a color filter for a solid-state imaging device such as a CCD, in order to achieve high resolution, it has been conventionally studied to use a dye instead of a pigment as a colorant (for example, see Patent Document 1). However, the dye-containing colored curable composition has the following new problems. That is,
(1) A dye that is in a molecularly dispersed state is generally inferior in light resistance and heat resistance compared to a pigment that is a molecular assembly.
(2) A dye that is in a molecularly dispersed state is generally inferior in solvent resistance compared to a pigment that is a molecular assembly.
(3) The dye often exhibits an interaction with other components in the colored curable composition, and the solubility (developability) between the cured part (exposed part) and the non-cured part (non-exposed part). Is difficult to adjust,
(4) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be used. For that purpose, a polymerizable compound (monomer), a binder, a photopolymerization initiator, etc. in the colored curable composition The other components must be reduced, and the curability of the colored curable composition, the heat resistance after curing, the developability of the non-cured portion, and the like are reduced.

Among these problems of dyes, dipyrromethene metal complexes have been studied as dyes that solve the problems of (1) light resistance and heat resistance of dyes and (4) molar extinction coefficient (ε) of dyes ( For example, see Patent Document 2).
A dipyrromethene metal complex is known to have characteristics such as excellent light resistance and heat resistance, a high molar extinction coefficient (ε), and favorable absorption characteristics in terms of color reproducibility (see, for example, Patent Document 2). As a functional compound in addition to a sensitizer as a radical polymerization initiator in a color filter used for a liquid crystal display device, a solid-state imaging device, or the like (for example, see Patent Document 2) and a polymerizable composition that is polymerized with visible light. Are also used (see, for example, Patent Documents 3 to 9).

  In order to improve solubility and the like, a porphyrin compound having a substituent having a steric parameter of 0.5 or more has been proposed (see, for example, Patent Document 10). However, although the solubility is improved, the heat resistance and the like are insufficient.

JP-A-6-75375 US Patent Application Publication No. 2008/0076044 Japanese Patent No. 3279035 Japanese Patent No. 3324279 Japanese Patent Laid-Open No. 11-352685 JP-A-11-352686 JP 2000-19729 A JP 2000-19738 A JP 2002-236360 A JP 2005-313632 A

However, colored curable compositions containing a dipyrromethene compound as a dye have been required to have better light resistance, heat resistance, and alkali resistance. Here, the alkali resistance means that when a colored curable composition layer is formed, if the layer comes into contact with an alkaline solution as a developer, the dye as a colorant is decolored or discolored by decomposition or dissolution by the developer. That means.
Further, as described in the above problem (2), in order to use a dye as a coloring component, it has been required to improve the solvent resistance. The solvent resistance is a performance in which the coloring component in the patterned cured portion is retained in the pattern of the patterned cured portion without eluting into the solvent. When an RGB color filter is manufactured by the photolithography method, a resist solution having a different hue is covered on the colored pattern in order to sequentially form each color pattern. At that time, if the coloring component in the cured part is dissolved into the colored curable composition of the next color, a problem of color mixing occurs. Therefore, in the color filter manufacturing process, very high solvent resistance is required in the cured part. In this respect, the dye is in a molecularly dispersed state, and is inferior in solvent resistance as compared with a pigment forming an aggregate with a strong intermolecular force.
Furthermore, in the production of a color filter, heat treatment may be performed after the coating, exposure, and development steps in order to increase the degree of curing of the colored pattern. Compared to pigments that are molecular aggregates, dyes that are in a molecularly dispersed state can move with small thermal energy, so they easily transfer to adjacent patterns with different hues, and the fixation of the dye in the cured area is a major issue. there were.

This invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a coloring compound having excellent heat resistance and alkali resistance and good color purity.
Furthermore, the present invention provides a dipyrromethene metal complex compound suitable as the dye compound, and a method for producing a dye multimer containing the dipyrromethene metal complex as a partial structure of the dye, and is suitable for providing a dipyrromethene metal complex compound in the production method. It is to provide a substituted pyrrole compound.

  As a result of detailed examinations of various dyes, the present inventors have found that a dye compound having a specific structure has a good hue and a high extinction coefficient, and is excellent in fastness such as solvent solubility, heat resistance, and light resistance. In particular, a dye multimer comprising a dipyrromethene dye compound as a constituent unit, a dye compound comprising a dipyrromethene metal complex, and a dye compound that functions as a polymerization component when a polymerizable group is introduced into the dipyrromethene dye compound to form a colored curable composition. As a result, the knowledge that it has high solvent resistance and heat resistance was obtained. The present invention has been achieved based on such findings.

Specific means for solving the above problems are as follows.
<1> A dye compound having a partial structure represented by the following general formula (5).

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents an integer of 1 to 8. When p is 2 or more, the structures in parentheses may be the same or different.R represents a hydrogen atom or a monovalent substituent.)

<2> The dye compound according to <1>, wherein the partial structure represented by the general formula (5) is a partial structure represented by the following general formula (6).

(In General Formula (6), Dye represents a dye structure, G ¹ represents a nitrogen atom or an oxygen atom, G ³ represents a carbon atom, a sulfur atom, an oxygen atom, or a nitrogen atom. P represents 1 or 2) , When p is 2, the structures in parentheses may be the same or different.)

<3> Dye in the general formula (5) is an azo dye, azomethine dye, dipyrromethene dye, quinone dye, carbonium dye, quinoneimine dye, azine dye, polymethine dye, quinophthalone dye, phthalocyanine dye, perinone dye, indigo dye, The dye compound according to <1> or <2>, which is a residue of a dye compound selected from the group consisting of a thioindigo dye, a quinoline dye, a nitro dye, a nitroso dye, and a metal complex compound thereof.

<4> Any one of <1> to <3>, wherein Dye in the general formula (5) is a residue of a dipyrromethene compound, or a residue of a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound The dye compound according to Item 1.

<5> The dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound, or a tautomer thereof, according to <4> Pigment compound.

(In the general formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent, and at least one substituent of R ^{4 to} R ¹⁰ is the same as G ¹ in the general formula (5). (However, R ⁴ and R ⁹ are not bonded to each other to form a ring.)

<6> The dipyrromethene metal complex compound obtained from the dipyrromethene compound of the general formula (M) and a metal or a metal compound, and a tautomer thereof are represented by the following general formula (7) or the general formula (8). The dye compound according to <4> or <5>, which is a dipyrromethene metal complex compound or a tautomer thereof.

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2. When a is 2, the structures of X ³ are the same or different. May be.)

<7> The dye compound according to <6>, wherein R ¹¹ and R ¹⁶ in the general formula (8) are each independently a monovalent substituent having a steric parameter -Es' value of 1.5 or more.

<8> The dye compound according to any one of <1> to <7>, further having a polymerizable group.

<9> Ma in Formula (7) or Formula (8) is any one of Zn, Co, V═O, or Cu, or any one of <6> to <8>. Dye compounds.

<10> The dye compound according to any one of <6> to <9>, wherein Ma in the general formula (7) or the general formula (8) is Zn.

<11> The dye compound according to any one of <1> to <10>, further having an alkali-soluble group.

<12> A dye compound which is a dye multimer containing a group obtained by removing 1 to 10 hydrogen atoms from the dye compound according to any one of <1> to <11> as a partial structure of the dye part.

<13> At least one of the structural units represented by the following general formula (A), general formula (B), and general formula (C) is included, or is represented by the following general formula (D). <12> The dye compound according to <12>.

(In General Formula (A), X ^A1 represents a linking group formed by polymerization, and L ^A1 represents a single bond or a divalent linking group. Dye II is derived from the partial structure represented by General Formula (5). A linking group having a structure in which 1 to (m1 + 1) hydrogen atoms are removed, and Dye in the general formula (5) is obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound It is a dye structure obtained by removing 1 to p arbitrary hydrogen atoms of a dipyrromethene metal complex compound, p represents 1 or 2, X ^A2 represents a linking group formed by polymerization, and L ^A2 represents a single bond or a divalent group. M1 represents an integer of 0 to 3. When m1 is 2 or more, [
The structure in] may be the same or different. DyeII the and L ^A2, covalent bonds are linked by either an ionic bond, and coordinate bond. )

(In the general formula (B), X ^B1 represents a linking group formed by polymerization, L ^B1 represents a single bond or a divalent linking group, and A represents a group capable of ionic bond or coordinate bond with DyeIII. DyeIII is a linking group having a structure obtained by removing 1 to (m2 + 1) hydrogen atoms from the partial structure represented by the general formula (5), and the Dye in the general formula (5) is represented by the following general formula (M ) Is a dye structure in which p hydrogen atoms have been removed from a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound, wherein p represents 1 or 2. X ^B2 is formed by polymerization. L ^B2 represents a single bond or a divalent linking group, and m2 represents an integer of 0 to 3. When m2 is 2 or more, the structures in [] are the same or different. also a good .DyeIII and ^{L B} And is a covalent bond, are connected in any of ionic bond, and coordinate bond.)

(In the general formula (C), L ^C1 represents a single bond or a divalent linking group. DyeIV is a linking group having a structure in which two hydrogen atoms are removed from the partial structure represented by the general formula (5). And Dye in the general formula (5) is a dye structure in which p hydrogen atoms of a dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the following general formula (M) and a metal or metal compound are removed. P represents 1 or 2. m3 represents an integer of 1 to 4. When m3 is 2 or more, L ^C1 may be the same or different.

(In General Formula (D), L ^D1 represents an m4-valent linking group, and m4 represents an integer of 2 to 100. When m4 is 2 or more, the structures of DyeV may be the same or different. DyeV is a linking group having a structure in which one hydrogen atom is removed from the partial structure represented by the general formula (5), and Dye in the general formula (5) is represented by the following general formula (M). (A dye structure in which p hydrogen atoms have been removed from a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. P represents 1 or 2.)

(In General Formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent, and a hydrogen atom is removed from at least one substituent of R ^{4 to} R ¹⁰ , provided that R ⁴ And R ⁹ are not bonded to each other to form a ring.)

<14> The dye compound according to <13>, wherein the structural unit represented by the general formula (A) is a structural unit derived from a dye monomer represented by the following general formula (1).

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound having a structure in which two hydrogen atoms are removed from the partial structure, and wherein Dye in the general formula (5) is represented by the following general formula (7) or (8): A dye structure in which p hydrogen atoms have been removed from the dipyrromethene metal complex compound obtained from 1. p represents 1 or 2. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. metal atom, or a metal compound represented .R ^18, R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group .R ¹¹ of or an arylsulfonyl group, And R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. of X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2.

<15> The dye compound according to <14>, which includes a monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond as a copolymerization component.

<16> The dye compound according to any one of <12> to <15>, further having an alkali-soluble group.

<17> A dye multimer comprising at least one of the structural units represented by the general formula (A), the general formula (B), and the general formula (C), represented by the general formula (D). The dye multimer, the dye monomer represented by the general formula (1), and the dye monomer represented by the general formula (1) are different in structure and have a single ethylenically unsaturated bond. <16> The dye compound according to <16>, wherein at least one selected from the group consisting of monomers has an alkali-soluble group.

<18> DyeII in the general formula (A), DyeIII in the general formula (B), DyeIV in the general formula (C), DyeV in the general formula (D), or DyeVI in the general formula (1). The dye compound according to <16> or <17>, which has an alkali-soluble group.

<19> Any one of <12> to <18> containing a polymerizable group introduced by adding a compound having a polymerizable group and a group that reacts with a substituent contained in the dye compound to the dye compound The dye compound according to Item 1.

<20> A dipyrromethene metal complex compound represented by the following general formula (I) by reacting a dipyrromethene compound represented by the following general formula (XI) with a metal derivative represented by the following general formula (XIII) A process for producing a dipyrromethene metal complex compound.

(In General Formula (I), G ⁴ and G ⁶ each independently represent a monovalent substituent having a steric parameter of -Es ′ value of 1.5 or more. R ³² , R ³³ , R ³⁵ , and R ³⁶ each independently represent a hydrogen atom, or ^{.R 37} representing a monovalent substituent include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic represents a group ^{.R 31, R 34} are each independently hydrogen Represents an atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, Ma represents a metal atom or a metal compound, and X ³ represents a group capable of bonding to Ma. And a represents 0, 1, or 2.)

(In the general formula ^{(XI), R} 31 ~R ³⁷ and ^G 4, ^{G 6} are the same respectively ^R 31 ^{to R 37} and ^G 4, ^{G 6} in the general formula (I).)

(In General Formula (XIII), Ma and X ¹ are respectively synonymous with Ma and X ¹ in General Formula (I). B represents an integer of 1 to 4.)

<21>
The compound represented by the following general formula (V) and the compound represented by the following general formula (X) are reacted to obtain the dipyrromethene compound represented by the above general formula (XI) <20> A method for producing a dipyrromethene metal complex compound.

(In the general formula ^(V), R ^31, R ^{32, R 33,} and ^{G 4} is ^R 31 in the general formula ^(I), R ^32, R 33, and ^{G 4} are each synonymous.)

(In the general formula ^{(X), R 34, R} 35, R 36, R 37, and ^{G 6} is, ^R 34 in the general formula ^{(I), R 35, R} 36, R 37, and a ^{G 6} respectively synonymous is there.)

<22> The method for producing a dipyrromethene metal complex compound according to <21>, wherein a compound represented by the general formula (X) is obtained by reacting a compound represented by the following general formula (IX) with an acylating agent. .

(In the general formula ^{(IX), R 34, R} 35, R 36, and ^{G 6} is ^{R 34, R 35, R 36} in the general formula (I), and a ^{G 6} respectively the same.)

<23> By reacting the compound represented by the following general formula (V), the compound represented by the following general formula (IX), and the compound represented by the following general formula (XII), Formula (XI)
<22> The manufacturing method of the dipyrromethene metal complex compound as described in <22> which obtains the dipyrromethene compound represented by these.

(In the general formula ^{(V), R 31, R} 32, R 33, and ^{G 4, R} 31 in the general formula ^{(I), R 32, R} 33, and ^{G 4} as the same meaning.)

(In the general formula ^{(IX), R 34, R} 35, R 36, and ^{G 6} is, ^R 34 in the general formula ^{(I), R 35, R} 36, and ^{G 6} as the same meaning.)

(In the general formula ^{(XII), R 37} has the same meaning as ^{R 37} in the general formula (I) ^{.R 38}
Represents an alkyl group or an aryl group. )

<24> A substituent G ⁴ in the compound represented by the general formula (V) is formed by chemically converting the leaving group X ¹¹ in the compound represented by the following general formula (IV) to a substituent. And the manufacturing method of the dipyrromethene metal complex compound of any one of <21>-<23> which obtains the compound represented by the said general formula (V).

(In the general formula ^(IV), R ^31, R ^{32, R 33} carbon atoms ^{.R 39} and ^{R 40} respectively and ^{R 31,} R ^{32, R 33} is as defined in formula (I) are each independently 2 The above alkyl group, alkenyl group, aryl group, and heterocyclic group are represented, X ¹¹ represents a monovalent leaving group, and n represents an integer of 0 to 10.)

<25> A compound represented by the general formula (IV) is obtained by reacting a compound represented by the following general formula (II) with a compound represented by the following general formula (III) <24> The manufacturing method of the dipyrromethene metal complex compound as described in 2.

(In the general formula ^(II), R ^31, R ^{32, R 33} are each synonymous with ^{R 31,} R ^{32, R 33} in the general formula (I).)

(In the general formula (III), R ³⁹ , R ⁴⁰ , X ¹¹ and n are R ³ in the general formula (IV).
⁹ , R ⁴⁰ , X ¹¹ and n are synonymous. X ¹² represents a monovalent leaving group. )

<26> A method for producing a dye multimer comprising synthesizing a dye multimer comprising a structural unit derived from a dye monomer represented by the following general formula (1) by radical polymerization.

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound having a structure in which two hydrogen atoms are removed from the partial structure, and wherein Dye in the general formula (5) is represented by the following general formula (7) or (8): A dye structure in which p hydrogen atoms have been removed from the dipyrromethene metal complex compound obtained from 1. p represents 1 or 2. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2. When a is 2, the structures of X ³ are the same or different. May be.)

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents an integer of 1 to 8. When p is 2 or more, the structures in parentheses may be the same or different.R represents a hydrogen atom or a monovalent substituent.)

<27> A dye monomer represented by the following general formula (1) is homopolymerized, or a dye monomer represented by the following general formula (1) and a single dye represented by the following general formula (1) A multimer is obtained by copolymerization with a monomer having a different structure and having a terminal ethylenically unsaturated bond, and then a compound having a group capable of reacting with the multimer and a polymerizable group is obtained. A method for producing a polymerizable group-containing dye multimer in which a polymerizable group is introduced by adding to a body.

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound having a structure in which two hydrogen atoms are removed from the partial structure, and wherein Dye in the general formula (5) is represented by the following general formula (7) or (8): A dye structure in which p hydrogen atoms have been removed from the dipyrromethene metal complex compound obtained from 1. p represents 1 or 2. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2. When a is 2, the structures of X ³ are the same or different. May be.)

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents an integer of 1 to 8. When p is 2 or more, the structures in parentheses may be the same or different.R represents a hydrogen atom or a monovalent substituent.)

<28> A substituted pyrrole compound represented by the following general formula (V).

(In the general formula (V), R ³² and R ³³ each independently represents a hydrogen atom or a monovalent substituent. R ³¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group. Represents an alkylsulfonyl group or an arylsulfonyl group, and G ⁴ represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more.)

<29> A substituted pyrrole compound represented by the following general formula (X).

(In the general formula (X), R ³⁵ and R ³⁶ each independently represents a hydrogen atom or a monovalent substituent. R ³⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group. Represents an alkylsulfonyl group or an arylsulfonyl group, R ³⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and G ⁶ represents a steric parameter -Es ′ value of 1. Represents a monovalent substituent of 5 or more.)

  Since the dye compound in the present invention has good heat resistance and color purity, it is effective as a dye for ink-jet ink, dye for sublimation type thermal transfer system, and the like. Furthermore, since the alkali resistance is excellent, the pixel pattern is formed in a thin film (for example, a thickness of 1 μm or less), and the minute size of 2 μm or less (the side length of the pixel pattern viewed from the normal direction with respect to the substrate is, for example, 0.5 It is particularly effective as a coloring matter used in a coloring composition for a color filter used in a color separation filter of a solid-state imaging device that requires a high-definition (˜2.0 μm) and has a rectangular cross-sectional profile.

According to the present invention, it is possible to provide a coloring compound having excellent heat resistance and alkali resistance and good color purity.
Further, it is possible to provide a dipyrromethene metal complex compound suitable as the dye compound, and a method for producing a dye multimer containing the dipyrromethene metal complex as a partial structure of the dye, and suitable for providing the dipyrromethene metal complex compound in the production method. A novel substituted pyrrole compound can be provided.

Below, the manufacturing method of the pigment | dye compound of this invention, the dipyrromethene metal complex compound, the manufacturing method of a pigment | dye multimer, and a substituted pyrrole compound are explained in full detail. The description of the constituent elements described below is made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, the “alkyl group” refers to a “straight chain, branched, and cyclic” alkyl group, and may be substituted or unsubstituted.

<Dye compound>
The dye compound of the present invention is a dye compound having a partial structure of the general formula (5) and having at least one substituent having a steric parameter of -Es' value of 1.5 or more. The steric parameter in the present invention is a parameter representing the steric bulk of the substituent, and the literature (JAMacphee, et al, Tetrahedron, Vol. 34, pp3553-3562, edited by Ikuo Fujita, Chemical Extension 107, Structure-Activity Relationship and Drug Design, -Es' value shown in February 20, 1986 (Chemical Doujin)) is used.
The dye compound of the present invention is a dye compound having a partial structure of the general formula (5), having at least one substituent having a steric parameter of -Es 'value of 1.5 or more, and an -Es' value. Is preferably 2.0 or more, more preferably 3.0 or more, still more preferably 4.0 or more, and particularly preferably 5.0 or more.
In the present invention, the decomposition of the amide bond or ester bond of the dye compound is suppressed by having a substituent having a steric parameter (-Es' value) of 1.5 or more in the vicinity of the amide bond or ester bond. It is considered that the heat resistance is improved.
The substituent may be specified using a steric parameter other than the -Es' value, but this does not impair the present invention.
Specific examples of the substituent having a steric parameter -Es' value of 1.5 or more are given below, but the present invention is not limited thereto.

In the substituents G ² in the general formula of the dye compound in the present invention (5), the substituents -Es' value is more than 1.5 of the further optional hydrogen atom on the substituents on any substituent May be substituted.
The dye compound of the present invention is a dye compound having a partial structure represented by the following general formula (5).

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents 1 to 8, preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 2. When p is 2 or more, the structures in parentheses may be the same or different. Represents a hydrogen atom or a monovalent substituent.)

  Preferably, the partial structure represented by the general formula (5) is a dye compound having a partial structure of the following general formula (11).

(In General Formula (11), Dye represents a dye structure, G ¹ represents a nitrogen atom or an oxygen atom, G ³ represents a carbon atom, a sulfur atom, an oxygen atom, or a nitrogen atom, and R ²⁴ and R ²⁵ each represent Independently represents an alkyl group, alkenyl group, aryl group or heterocyclic group having 2 or more carbon atoms, p represents an integer of 1 to 8, and when p is 2 or more, the structures in parentheses may be the same or different; Good.)

More preferably, it is a dye compound in which the partial structure represented by the general formula (5) is a partial structure of the following general formula (6).
The general formulas (5), (6), and (11) represent partial structures of the dye structure of the present invention, and include a dye compound in which an arbitrary hydrogen atom is replaced with an arbitrary substituent.

(In General Formula (6), Dye represents a dye structure, G ¹ represents a nitrogen atom or an oxygen atom, G ³ represents a carbon atom, a sulfur atom, an oxygen atom, or a nitrogen atom. P represents 1 or 2) , When p is 2, the structures in parentheses may be the same or different.)

There is no restriction | limiting in particular as a dye structure represented by Dye in this invention, The various thing containing a well-known dye structure can be used. Known dye structures include, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane). Dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, cyanine dyes) Among them, squarylium dye, croconium dye, etc.), quinophthalone dye, phthalocyanine dye, perinone dye, indigo dye, thioindigo dye, quinoline dye, nitro dye, nitro Dyes, and the like can be given their metal complex dye. Among these dye structures, azo dyes, azomethine dyes, dipyrromethene dyes, quinone dyes (particularly anthraquinone dyes), carbonium dyes (particularly xanthene dyes), and polymethine dyes (particularly cyanine dyes, oxonol dyes) are preferable. A dye, an azomethine dye, and a polymethine dye are more preferable, and a dipyrromethene dye is particularly preferable. For specific compounds, please refer to “New edition Dye Handbook” (Organic Synthetic Chemistry Association; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Dye Handbook” (Okawara et al .; Kodansha, 1986), etc. It is described in.

In these dyes, the introduction of a substituent having an -Es' value of 1.5 or more of the present invention can be selected at any substitution position, but from the viewpoint of improving the stability of the spectral characteristics of the dye, the position adjacent to the chromophore. Alternatively, it is preferably introduced at the conjugate position, and most preferably applied to an auxiliary color group that has a great influence on the maximum absorption wavelength (λmax) and the molar light absorption coefficient. Or it is most preferable to introduce into a substituent on an atom having a large coefficient of HOMO and LUMO obtained by molecular orbital calculation, particularly a substituent on an atom having a large difference in coefficient of HOMO and LUMO.
Specific pigments to which the present technology is preferably applied will be described in detail below.

<Dipyrromethene compound>
The dye compound of the present invention is preferably a dipyrromethene compound, a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound.
The above-described dipyrromethene metal complex compound is preferably a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound, and a tautomer thereof. It is a pigment compound derived from the dipyrromethene metal complex compound represented by the general formula (7) or the dipyrromethene metal complex compound represented by the general formula (8).

[Dipyrromethene metal complex compound obtained from dipyrromethene compound represented by general formula (M) and metal or metal compound and tautomer thereof]
One of preferable embodiments of the dye compound of the present invention is a complex in which a compound represented by the following general formula (M) (dipyrromethene compound) or a tautomer thereof is coordinated to a metal or a metal compound (hereinafter referred to as “ This is a dye compound containing a “specific complex”) as a dye moiety.
In the present invention, a compound containing a dipyrromethene structure is referred to as a dipyrromethene compound, and a metal or a complex coordinated to a metal compound is referred to as a dipyrromethene metal complex compound.

In the general formula (M), R ^{4 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent, and at least one substituent among R ^{4 to} R ¹⁰ is G ¹ in the general formula (5). Concatenate with However, R ⁴ and R ⁹ are not bonded to each other to form a ring.

Examples of the monovalent substituent when R ^{4 to} R ⁹ in the general formula (M) represent a monovalent substituent include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group ( Preferably a straight, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 18 carbon atoms) Groups such as vinyl, allyl, 3-buten-1-yl), aryl groups (preferably having 6 to 48 carbon atoms, More preferably, it is an aryl group having 6 to 24 carbon atoms, such as phenyl or naphthyl, and a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2- Thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably having 3 to 38 carbon atoms) Preferably a silyl group having 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably carbon An alkoxy group having 1 to 48, more preferably 1 to 24 carbon atoms, for example, methoxy, ethoxy 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably having 6 to 48 carbon atoms, more preferably carbon An aryloxy group having 6 to 24, for example, phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, -Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

Silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably having 2 carbon atoms) 48, more preferably an acyloxy group having 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms). 24 alkoxycarbonyloxy groups such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy groups such as cyclohexyloxycarbonyloxy, aryloxycarbonyloxy groups (preferably Is an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 1 carbon atoms). 24 carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy groups (preferably having a carbon number) 1 to 32, more preferably a sulfamoyloxy group having 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably having a carbon number) 1 to 38, more preferably 1 to 24 carbon In Niruokishi group, e.g., methylsulfonyloxy, hexadecyl sulfonyloxy, cyclohexyl sulfonyloxy)

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) Examples of carbonyl groups include methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), and aryloxycarbonyl groups (preferably having 7 to 32 carbon atoms). , Yo Preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (Preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino),

Anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms such as anilino and N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). A heterocyclic amino group such as 4-pyridylamino), a carbonamido group (preferably having a carbon number of 2 to 48, more preferably 2 to 24, such as acetamide, benzamide, tetradecanamide, pivaloylamide, cyclohexane Amide), ureido groups (preferably ureido groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide groups (preferably carbon An imide group having 36 or less, more preferably 24 or less carbon atoms, for example, N-succi Imide, N-phthalimide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino , Octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), sulfone An amide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfone; Amide, cyclohexanesulfonamido), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N -Ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo, 3-pyrazolylazo),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) An ylamino group represents, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

In the case where the monovalent substituents represented by R ^{4 to} R ⁹ in the general formula (M) are further substitutable groups, the substituents described for R ^{4 to} R ⁹ may be further included. In the case of having two or more substituents, these substituents may be the same or different.

R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ in the general formula (M) are independently bonded to each other to form a 5-membered, 6-membered, or 7-membered compound. A membered saturated ring or an unsaturated ring may be formed. When the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may be substituted with the substituents described for R ^{4 to} R ⁹ above, and two or more When substituted with a substituent, these substituents may be the same or different.
R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ in the general formula (M) are each independently bonded to each other and have no substituent. In the case of forming a 6-membered or 7-membered saturated ring or an unsaturated ring, examples of the 5-membered, 6-membered or 7-membered saturated ring or unsaturated ring having no substituent include, for example, a pyrrole ring, Furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring, preferably , A benzene ring and a pyridine ring.

R ¹⁰ in the general formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and examples of the halogen atom, alkyl group, aryl group, and heterocyclic group include the R ⁴ those described with substituents to R ⁹ and have the same meanings, thereof are also the same preferable ranges.
When R ¹⁰ represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group, aryl group, and heterocyclic group are further substitutable groups, the above-mentioned R ^{4 to} R ⁹ It may be substituted with the substituent described for the monovalent substituent, and when substituted with two or more substituents, these substituents may be the same or different.

~ Metal or metal compound ~
The specific complex in the present invention is a complex in which the compound represented by the general formula (M) described above or a tautomer thereof is coordinated to a metal or a metal compound.
Here, the metal or metal compound may be any metal or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, Or a bivalent metal chloride is contained. Examples of the metal or metal compound include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and the like, as well as AlCl, InCl, FeCl, TiCl2, and SnCl2. Further, metal chlorides such as SiCl 2 and GeCl 2, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex VO is preferred, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferred, and Zn is most preferred.

Next, the further preferable range of the specific complex in the present invention of the compound represented by the general formula (M) will be described.
The preferred range of the specific complex in the present invention is that in general formula (M), R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group , An aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R ⁵ and R ⁸ are Each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, Reel group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group , A sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom or a halogen atom. , Alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamide Group, ureido group, imide group, Alkoxycarbonyl amino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group, R ¹⁰ is a hydrogen atom , A halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or V = O It is a certain range.

A more preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, or an acyl group. , Alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl A phosphinoylamino group, and R ⁵ and R ⁸ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxy group Carbonyl group, carbamoyl group, imide group, alkylsulfonyl group, aryl R ⁶ and R ⁷ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group , Carbonamide group, ureido group, imide group, alkoxycarbonylamino group, sulfonamido group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group, and R ¹⁰ is hydrogen. It is represented by an atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the metal or metal compound is in a range where Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V = O. .

The particularly preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, A carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R ⁵ and R ⁸ are each independently It is represented by an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl A group, an aryl group, or a heterocyclic group, and R ¹⁰ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring It is represented by a group, and the metal or metal compound is in a range where Zn, Cu, Co, or V = O.
Furthermore, the embodiment represented by the general formula (7) or the general formula (8) described in detail below is also a particularly preferable embodiment.

[Dipyrromethene metal complex compound represented by general formula (7)]
One embodiment of the dye compound of the present invention is a dipyrromethene metal complex compound represented by the following general formula (7).

In the general formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ¹ represents a group that can be bonded to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other with Ma to form a 5-, 6-, or 7-member. The ring may be formed. However, R ⁴ and R ⁹ are not bonded to each other to form a ring.
In addition, the dipyrromethene metal complex compound represented by the general formula (7) includes a tautomer.

The dipyrromethene metal complex compound represented by the general formula (7) is a structural unit represented by the general formula (A) to the general formula (C) described later, a multimer represented by the general formula (D), or The introduction site for introduction into the monomer represented by the general formula (1) is not particularly limited, but it should be introduced at any one of R ^{4 to} R ^{9 from} the viewpoint of synthesis compatibility. It is more preferable that it is introduced at any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ , and it is even more preferred that it is introduced at any one of R ⁴ and R ⁹ .

As a method for introducing an alkali-soluble group into the dye compound of the present invention, any one or more of R ^{4 to} R ¹⁰ , X ¹ and X ² of the dipyrromethene metal complex compound represented by the general formula (7) is used. These substituents can have an alkali-soluble group. Among these substituents, any ^one of R ^{4 to} R ⁹ and X ¹ is preferable, any of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and any of R ⁴ and R ⁹ is still more preferable.

The dipyrromethene metal complex compound represented by the general formula (7) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.
^R 4 to R ⁹ in the middle in the general formula (7) has the same meaning as ^R 4 to R ⁹ in the general formula (M), preferable embodiments thereof are also the same.

In the general formula (7), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included.
For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe , etc., and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl 2 , etc. Metal chlorides, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are included.

  Among these, from the viewpoints of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and V = O are preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and V = O are more preferable, and Zn, Co, V = O, and Cu are particularly preferable Zn is most preferred.

In the general formula (7), R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom.

In the general formula (7), X ¹ may be any group as long as it is a group capable of binding to Ma. Specifically, water, alcohols (for example, methanol, ethanol, propanol), etc. The compounds described in “Metal Chelate” ([1] Takeichi Sakaguchi / Keihei Ueno (1995 Nanedo), [2] (1996), [3] (1997), etc.) can be mentioned. Among these, from the viewpoint of production, water, carboxylic acid compounds and alcohols are preferable, and water and carboxylic acid compounds are more preferable.

In the general formula (7), examples of the “group that neutralizes the charge of Ma” represented by X ² include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group. From the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.

In the general formula (7), X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings may be composed of only carbon atoms, and form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom. You may do it.

As a preferred embodiment of the compound represented by the general formula (7), R ^{4 to} R ⁹ are each independently a preferred embodiment described in the description of R ^{4 to} R ⁹ , and R ¹⁰ is a description of R ¹⁰ . In the preferred embodiment described, Ma is Zn, Cu, Co, or V = O, X ¹ is water or a carboxylic acid compound, X ² is a hydroxyl group or a carboxylic acid group, and X ¹ and X ² may be bonded to each other to form a 5-membered or 6-membered ring.

[Dipyrromethene metal complex compound represented by general formula (8)]
One embodiment of the dye compound of the present invention is a dipyrromethene metal complex compound represented by the following general formula (8).

In general formula (8), R ¹¹ and R ¹⁶ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. To express. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent. R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. R ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or A 7-membered ring may be formed. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2. In addition, the dipyrromethene metal complex compound represented by the general formula (8) includes a tautomer.

Formula site for introducing the dye multimer below the dipyrromethene metal complex compound represented by (8) is unless not particularly limited to impair the effects of the present ^{invention, R 11 ~R 16, X 3} , R 18 it is preferable that any one of to R ^19. Among these, from the viewpoint of synthesis ^suitability, it is preferable to introduced at any one of R 11 ^{to R 16} and ^{X 3,} more ^preferably, one of R ^11, R ^{13, R 14} and ^{R 16} It is an embodiment inserted in one, and more preferably an embodiment inserted in any one of R ¹¹ and R ¹⁶ .

As a method for introducing an alkali-soluble group into the dye compound of the present invention, when a dye monomer or a structural unit having an alkali-soluble group is used, R ^{11 to} R of the dipyrromethene metal complex compound represented by the general formula (8) Any one or two or more substituents of ¹⁷ , X ³ , R ^{18 to} R ¹⁹ can have an alkali-soluble group. Among these substituents, any one of R ^{11 to} R ¹⁶ and X ³ is preferable, any of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ is more preferable, and any of R ¹¹ and R ¹⁶ is still more preferable.

  The dipyrromethene metal complex compound represented by the general formula (8) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.

Said R < ¹² > -R < ¹⁵ > is synonymous with R < ⁵ > -R < ⁸ > in the said general formula (M), and its preferable aspect is also the same. R ¹⁷ has the same meaning as R ¹⁰ in the general formula (M), and the preferred embodiment is also the same. Said Ma is synonymous with Ma in the said General formula (7), and its preferable range is also the same.

More specifically, in the general formula (8), among R ^{12 to} R ¹⁵ , the R ¹² and R ¹⁵ include an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, Nitrile group, imide group or carbamoylsulfonyl group is preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl Group, carbamoyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferred, and alkoxycarbonyl group, aryloxycarbonyl group and carbamoyl group are particularly preferred.
R ¹³ and R ¹⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted. A substituted aryl group. Here, specific examples of more preferable alkyl groups, aryl groups, and heterocyclic groups can similarly include specific examples listed in R ⁶ and R ⁷ of the general formula (M).

In the general formula (8), R ¹¹ and R ¹⁶ are alkyl groups (preferably linear, branched or cyclic alkyl groups having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, triethylmethyl), an alkenyl group (preferably having 2 to 24 carbon atoms, More preferably, it is a C2-C12 alkenyl group, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably a C6-C36, more preferably a C6-C18 aryl group) And, for example, phenyl, naphthyl, o-tolyl), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably having carbon atoms) 1 to 12 heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl) An alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxy, ethoxy, propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy) An aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably an aryloxy group having 1 to 18 carbon atoms, such as phenoxy or naphthyloxy), an alkylamino group (preferably having 1 to 36 carbon atoms, more preferably An alkylamino group having 1 to 18 carbon atoms such as methylamino, ethyl Amino, propylamino, butylamino, hexylamino, 2-ethylhexylamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N- Dibutylamino, N-methyl-N-ethylamino), arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylamino, naphthylamino, N, N -Diphenylamino, N-ethyl-N-phenylamino), or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-aminopyrrole, 3-aminopyrazole, 2-aminopyridine, 3-aminopyridine).

Among the above, R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, and a heterocyclic amino group, and an alkyl group, an alkenyl group, an aryl group, Heterocyclic groups are more preferred, alkyl groups, alkenyl groups, and aryl groups are more preferred, and alkyl groups are particularly preferred.

In the general formula (8), R ¹⁸ and R ¹⁹ are a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms). , For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, More preferably, it is a C2-C12 alkenyl group, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably a C6-C36, more preferably a C6-C18 aryl group) And, for example, phenyl, naphthyl), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon hetero atoms). Groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl groups (preferably An acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably Is an alkylsulfonyl group having 1 to 18 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably arylsulfonyl having 6 to 18 carbon atoms) A group such as phenylsulfonyl, Phthalylsulfonyl).

Among the above, R ¹⁸ and R ¹⁹ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In the general formula (8), R ¹¹ and R ¹⁸ are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran). , Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, Cycloheptane, hexamethyleneimine).

In the general formula (8), R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran). , Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, Cycloheptane, hexamethyleneimine).

In the general formula (8), R ¹¹ and R ¹⁶ are each independently a monovalent substituent having a steric parameter -Es' value of 1.5 or more, preferably 2.0 or more. Is more preferably 3.5 or more, and particularly preferably 5.0 or more.

In the general formula (8), examples of the group capable of binding to Ma represented by X ³ include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a “metal chelate” ([1] Sakaguchi Takeichi and Ueno Keihei (1995 Nanedo), [2] (1996), [3] (1997), etc.). Among these, from the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a halogen atom, a hydroxyl group, and a carboxylic acid group are more preferable. a represents 0, 1, or 2. When a is 2, the structures of X ³ may be the same or different.

As a preferable aspect of the compound represented by the general formula (8), R ^{12 to} R ¹⁵ are each preferably a preferable aspect described in the description of R ^{5 to} R ^{8 in} the general formula (M). R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (M), Ma is Zn, Cu, Co, or V═O, and R ¹⁸ and R ¹⁹ are each independently a hydrogen atom. R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, or an aryl group having an -Es ′ value of 2.0 or more, and X ³ is a group bonded through an oxygen atom. Yes, a is 0 or 1. R ¹¹ and R ¹⁸ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and R ¹⁹ may be bonded to each other to form a 5- or 6-membered ring.

As a more preferable aspect of the compound represented by the general formula (8), R ^{12 to} R ¹⁵ are each preferably independently described in the description of R ^{5 to} R ⁸ in the compound represented by the general formula (M). R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (M), Ma is Zn, R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or an alkyl group. , R ¹¹ and R ¹⁶ are each independently an alkyl group, alkenyl group or aryl group having an -Es' value of 3.5 or more, X ³ is a group bonded via an oxygen atom, and a is 0 Or it is 1. R ¹¹ and R ¹⁸ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and R ¹⁹ may be bonded to each other to form a 5- or 6-membered ring.

The molar extinction coefficient of the dipyrromethene metal complex compound represented by the general formulas (7) and (8) is preferably as high as possible from the viewpoint of coloring power. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. By being in this region, it is possible to produce a color filter with good color reproducibility when applied to a colored curable composition or the like. Furthermore, the absorbance at the maximum absorption wavelength (λmax) is preferably 1,000 times or more, more preferably 10,000 times or more, more preferably 100,000 times the absorbance at 450 nm of the dye multimer of the present invention. More preferably, it is twice or more. When this ratio is in this range, when applying the dye multimer of the present invention to a colored curable composition or the like, it is possible to form a color filter with higher transmittance, particularly when producing a blue color filter. it can. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer carry5 (manufactured by Varian).
The melting point of the dipyrromethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably not too high from the viewpoint of solubility.

  The dipyrromethene metal complex compounds represented by the general formulas (7) and (8) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, and JP-A-2001-240761. 2002-155052 gazette, Japanese Patent No. 3614586 gazette, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like. Specifically, the method described in paragraphs 0131 to 0157 of JP-A-2008-292970 can be applied.

  Next, although the specific example of the dipyrromethene metal complex compound in this invention is shown below, this invention is not limited to these.

<Azo dye>
In the azo dye represented by the following general formula (9), when an acylamino group is introduced as an auxiliary color group or an acyloxy group is introduced as a substituent, the bulky acyl group of the present invention acts effectively.
Cp-N = ND (9)

In the general formula (9), Cp represents a coupling component, and D represents a diazo component. Examples of coupling components include aromatic hydrocarbon rings such as phenols, naphthols and anilines, heterocycles such as pyrazolones, aminopyridines and pyridones, and open-chain active methylene compounds. I can do it. Examples of the diazo component include a benzene ring, a naphthalene ring, and a heterocyclic ring (eg, thiazole, pyrazole, thiophene, imidazole). The bulky substituent of the present invention is preferably introduced into the conjugated position of the azo group (for example, in the case of a benzene ring or a pyridine ring, the 2-position or 4-position with respect to the azo group).
Specific examples of the azo dye represented by the general formula (9) are shown below, but the present invention is not limited thereto.

<Azomethine dye>

In the general formula (10), R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group, or an alkylamino group. Group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, carboxyl Represents a group or a sulfo group. E represents —NR ³⁵ R ³⁶ or a hydroxy group, and R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. E is preferably —NR ³⁵ R ³⁶ . R ³⁵ and R ³⁶ may be bonded to each other to form a ring. B ¹ represents = C (R ³³ )-or = N-, and B ² represents -C (R ³⁴ ) = or -N =. It is preferable that B ¹ and B ² are not simultaneously -N =, and it is more preferable that B ¹ is = C (R ³³ )-and B ² is -C (R ³⁴ ) =. R ³³ and R ³⁴ have the same meanings as R ³¹ and R ³² described above. R ³¹ and R ³⁵ , R ³³ and R ³⁶ and / or R ³¹ and R ³² may be bonded to each other to form an aromatic ring or a heterocyclic ring. X ⁵ represents a residue of an active methylene compound.

In the general formula (10), R ³² represents a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a sulfone among the above substituents. An amide group is preferred.
Specific examples of the azomethine dye represented by the general formula (10) are shown below, but the present invention is not limited thereto.

<Polymethine dye>
As polymethine dyes, oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, and styryl dyes as shown in the following general formula are known, and cyanine dyes include squarylium dyes and croconium dyes. Among these dyes, oxonol dyes and cyanine dyes are preferable, and cyanine dyes, particularly squarylium dyes are particularly preferable.

Cyanine dye: Bs = Lo-Bo
Merocyanine dye: Bs = Le = Ak
Arylidene dyes: Ak = Lo-Ar
Styryl dye: Bo-Le-Ar
Oxonol dye: Ak = Lo-Ae

Where Bs is a basic nucleus; Bo is an onium body of the basic nucleus; Ak is a keto-type acidic nucleus; Ae is an enol-type acidic nucleus; Ar is an aromatic nucleus Lo is a methine chain consisting of an odd number of methines; and Le is a methine chain consisting of an even number of methines. In the present invention, a monomethine dye consisting of Lo and one methine is also included in the polymethine dye.

Polymethine dyes are described in FMHarmer “Heterocyclic Compounds Cyanine Dyes and Related Compounds”, John Wiley and Sons. Sons, New York, London, 1964; DMSturmer, “Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry”, 18th. It can be synthesized with reference to Chapters, Section 14, and the description of JP-A-6-313939.
Although the specific example of a polymethine pigment | dye is shown below, this invention is not limited to these.

The dye compound of the present invention preferably further has a polymerizable group.
The method for introducing a polymerizable group into the dye compound of the present invention is not particularly limited, but an ethylenically unsaturated group (for example, methacryl group, acrylic group, styryl group, etc.), a cyclic ether group (for example, epoxy group, It can be introduced by adding a polymerizable compound having an oxetanyl group or the like to the dye compound.
Specifically, for example, a polymerizable compound (methacrylic chloride, acrylic chloride, 4- (chloromethyl) styrene is added to a dye compound having a group that reacts with the polymerizable compound (for example, hydroxyl group, amino group, carboxyl group, etc.). , Glycidyl methacrylate, methacryloxyethyl isocyanate, etc.) can be added to synthesize a dye compound having a polymerizable group.
By introducing a polymerizable group into the dye compound, curability, heat resistance, and solvent resistance are improved.

The dye compound of the present invention preferably further has an alkali-soluble group. When the dye compound has an alkali-soluble group, when it is used in a coloring composition for a color filter, the developability is good and the pattern shape is good.
The method for introducing an alkali-soluble group into the dye compound of the present invention is not particularly limited, but can be introduced by adding a compound having an alkali-soluble group to the dye compound.
Specifically, for example, a dye compound having a group that reacts with a compound having alkali solubility (for example, a halogenated alkyl group, an α-halogenated acyl group, etc.) and a compound having alkali solubility (for example, thiomalic acid, thiol Glycolic acid, 5-mercaptoisophthalic acid, 3-mercaptobenzoic acid, malic acid, glycolic acid, 5-hydroxyisophthalic acid, 3-hydroxybenzoic acid, etc.) are added to synthesize a coloring compound having an alkali-soluble group. be able to. By introducing an alkali-soluble group into the dye compound, the color pattern forming property is improved.

  The coloring matter compound of the present invention preferably contains an alkali-soluble group from the viewpoint of color pattern formation when applied to a colored curable composition, and preferably contains an acid value of 30 to 300 mgKOH / g. It is more preferable that the acid value is 50 to 200 mgKOH / g.

≪Dye multimer≫
The dye compound of the present invention is preferably a dye multimer containing the dye structure described above as a partial structure of the dye part. In particular, it may be a dye multimer containing a dye structure derived from a dipyrromethene compound as a partial structure of a dye part, or may be a dye multimer containing a dye structure derived from a dipyrromethene metal complex compound as a partial structure of a dye part. .
The method of introducing the dye skeleton derived from the dipyrromethene compound and the dipyrromethene metal complex compound into the dye multimer of the present invention is arbitrary, and a polymer obtained by introducing the dye skeleton into a polymerizable monomer is polymerized or copolymerized. A multimer may be obtained, and a dye skeleton may be introduced by polymer reaction or the like after the multimer is formed.
Preferred embodiments include a multimer comprising at least one structural unit represented by the above general formulas (A) to (C), a dye multimer represented by the above general formula (D), and the above general formula ( Examples include multimers containing the dye monomer represented by 1) as a polymerization component.

<Preferred physical properties of the dye multimer of the present invention>
The dye multimer of the present invention is excellent in color purity, light resistance, heat resistance, and solvent resistance, has little color transfer, and can form a cured film with good pattern moldability. It can be used in suitable colored curable compositions. From such a viewpoint, if the preferable physical properties of the dye multimer of the present invention are mentioned, when the dye multimer of the present invention is applied to a colored curable composition, the dye of the present invention is improved from the viewpoint of improving the color pattern forming property. The multimer preferably has an alkali-soluble group.

The method for introducing an alkali-soluble group into the dye multimer of the present invention is not particularly limited, but can be introduced by synthesizing a dye multimer using a monomer having an alkali-soluble group, An alkali-soluble group can be introduced after the dye multimer is synthesized.
When synthesizing a dye multimer using a monomer having an alkali-soluble group, at least one of the structural units represented by the general formula (A), the general formula (B), and the general formula (C) is used. A dye multimer comprising, a dye multimer represented by the general formula (D), a dye monomer represented by the general formula (1), and a single dye represented by the general formula (1) It is sufficient that at least one monomer having a structure different from that of the body and having a terminal ethylenically unsaturated bond has an alkali-soluble group.
The structural unit represented by the general formula (A), the general formula (B), and the general formula (C), or the dye monomer represented by the general formula (1) is a simple unit having an alkali-soluble group. When it is a monomer, it can have an alkali-soluble group in the Dye part (dye residue). From the viewpoint of synthetic compatibility, at least one other ethylenically unsaturated bond monomer contained as a copolymerization component is included rather than a monomer that forms a structural unit having a Dye portion (dye residue). A monomer having an alkali-soluble group is preferable.

The dye multimer of the present invention preferably contains an alkali-soluble group having an acid value of 10 to 400 mgKOH / g, and an acid value of 30 to 300 mgKOH / g, from the viewpoint of color pattern formation when applied to a colored curable composition. More preferably, the acid value is more preferably 50 to 200 mgKOH / g.
In the present invention, the acid value is determined by the method described in JIS standard (JIS K 0070: 1992).

  The dye multimer of the present invention preferably has a solubility in an alkaline solution (pH 9 to 15) as a developer of 0.1% by mass or more and 80% by mass or less, and is 0.5% by mass or more and 50% by mass. The content is more preferably 1% by mass or more and 30% by mass or more. By being in this region, when the dye multimer of the present invention is used for an application requiring alkaline development such as a colored curable composition, it is possible to form a suitable pattern shape and reduce residues on the substrate. It becomes like this.

In addition, when the dye multimer of the present invention is applied to a colored curable composition, the dye multimer of the present invention may have a polymerizable group from the viewpoint of suppressing color transfer and improving color pattern formation. preferable. The polymerizable group contained in the dye multimer may be one type or two or more types.
Examples of the polymerizable group include an ethylenically unsaturated group (for example, methacryl group, acrylic group, styryl group, etc.), a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) and the like. Among these, an ethylenically unsaturated group is preferable from the viewpoint of heat resistance and solvent resistance after polymerization.

The polymerizable group-containing dye multimer preferably includes, as a repeating unit, a constituent unit having a polymerizable group and a constituent unit having a group derived from the dye.
The polymerizable group-containing dye multimer may contain a constituent unit having a polymerizable group and a constituent unit other than a constituent unit having a group derived from a dye.
In the polymerizable group-containing dye multimer, from the viewpoint of thinning the color filter, it is preferable to include 60 mass% to 99 mass% of a structural unit having a group derived from the dye in a mass ratio of 70 mass%. It is more preferable to contain -97 mass%, and it is further more preferable to contain 80 mass%-95 mass%.
Further, from the viewpoint of heat resistance and solvent resistance, the structural unit having a polymerizable group is preferably contained in an amount of 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass. More preferably, the content is 20% by mass to 20% by mass.

The structural unit having a polymerizable group can be introduced into the polymerizable group-containing dye multimer by the following method, for example.
That is, a structure in which a multimer is obtained by copolymerization of the dye compound and a copolymer component having no dye skeleton (for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, etc.), and then derived from the copolymer component By adding a polymerizable compound having a group that reacts with the unit (for example, glycidyl methacrylate, methacryloxyethyl isocyanate, etc.), a structural unit having a polymerizable group can be introduced.
In the dye compound, a polymerizable group different from the polymerizable group for multimerization of the dye compound is introduced into the dye skeleton, and the dye compound is polymerized to obtain a polymerizable group-containing dye multimer. You can also get

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

  The Tg of the dye multimer of the present invention is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% mass reduction temperature by thermal mass spectrometry (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, it becomes possible to reduce a change in concentration caused by a heating process when the dye multimer of the present invention is applied to a colored curable composition or the like.

  The molar extinction coefficient of the dye multimer of the present invention is preferably as high as possible from the viewpoint of coloring power. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. By being in this region, it is possible to produce a color filter with good color reproducibility when applied to a colored curable composition or the like. Furthermore, the absorbance at the maximum absorption wavelength (λmax) is preferably 1,000 times or more, more preferably 10,000 times or more, more preferably 100,000 times the absorbance at 450 nm of the dye multimer of the present invention. More preferably, it is twice or more. When this ratio is in this range, when applying the dye multimer of the present invention to a colored curable composition or the like, it is possible to form a color filter with higher transmittance, particularly when producing a blue color filter. it can. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer carry5 (manufactured by Varian).

  Further, the extinction coefficient per unit weight of the dye multimer of the present invention (hereinafter referred to as ε ′; unit: L / g · cm) is preferably 30 or more, more preferably 60 or more, and 90 It is still more preferable that it is above. By being in this range, when applying the dye multimer of this invention to a coloring composition and producing a color filter etc., a color filter with favorable color reproducibility can be produced.

  Further, it is more preferable that the dye multimer of the present invention simultaneously satisfies the preferable ranges of the maximum absorption wavelength (λmax) and the extinction coefficient per unit weight of the dye multimer.

<Structure of the dye multimer of the present invention>
The dye multimer of the present invention is preferably a dye multimer having a dye skeleton derived from a dipyrromethene metal complex compound.
The dye multimer having a dye skeleton derived from the dipyrromethene metal complex compound includes at least one of structural units represented by the following general formula (A), general formula (B), and general formula (C). Or a dye multimer represented by the general formula (D), and a dye multimer containing a dye monomer represented by the following general formula (1) as a polymerization component. These will be described sequentially.

<Structural Unit Represented by General Formula (A)>

(In General Formula (A), X ^A1 represents a linking group formed by polymerization, and L ^A1 represents a single bond or a divalent linking group. Dye II is derived from the partial structure represented by General Formula (5). A linking group having a structure in which 1 to (m1 + 1) hydrogen atoms are removed, and Dye in the general formula (5) is obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound It is a dye structure obtained by removing 1 to p arbitrary hydrogen atoms of a dipyrromethene metal complex compound, p represents 1 or 2, X ^A2 represents a linking group formed by polymerization, and L ^A2 represents a single bond or a divalent group. M1 represents an integer of 0 to 3. When m1 is 2 or more, [
The structure in] may be the same or different. DyeII the and L ^A2, covalent bonds are linked by either an ionic bond, and coordinate bond. )

In the general formula (A), X ^A1 and X ^A2 each independently represent 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. ^Examples of X ^A1 and X ^A2 include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and preferably unsaturated. It is a linking group formed by polymerizing an ethylene group. Specific examples include the following linking groups, but the linking groups formed by polymerization in the present invention are not limited to these.
In addition, in the following (X-1)-(X-15), it represents having connected with ^LA1 in the site ^| part shown by *.

In general formula (A), L ^A1 represents a single bond or a divalent linking group. In the case where L ^A1 represents a divalent linking group, the divalent linking group is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group). Etc.), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S- , —NR— (wherein R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) —, —SO—, —SO ₂ —, A linking group represented by the following general formula (2), a linking group represented by the general formula (3), or a linking group represented by the general formula (4)), and two or more of these are linked. Represents a linking group to be formed.
The divalent linking group in the general formula (A) is not particularly limited as long as the effects of the present invention can be obtained.

In the general formula (A), a dye residue obtained by removing 1 to p arbitrary hydrogen atoms of a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound. Represents a group obtained by removing 1 to (m1 + 1) hydrogen atoms from the general formula (5). p represents 1 or 2.
Preferably, it is a dye structure in which m1 + 1 arbitrary hydrogen atoms of the dipyrromethene metal complex compound represented by the general formula (5) or the general formula (6) are removed.

  Although the specific example of the structural unit represented by general formula (A) is shown below, this invention is not limited to this.

<Structural Unit Represented by General Formula (B)>
Next, details of the structural unit represented by the general formula (B) will be described.

(In the general formula (B), X ^B1 represents a linking group formed by polymerization, L ^B1 represents a single bond or a divalent linking group, and A represents a group capable of ionic bond or coordinate bond with DyeIII. DyeIII is a linking group having a structure obtained by removing 1 to (m2 + 1) hydrogen atoms from the partial structure represented by the general formula (5), and the Dye in the general formula (5) is represented by the following general formula (M ) Is a dye structure in which p hydrogen atoms have been removed from a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound, wherein p represents 1 or 2. X ^B2 is formed by polymerization. L ^B2 represents a single bond or a divalent linking group, and m2 represents an integer of 0 to 3. When m2 is 2 or more, the structures in [] are the same or different. also a good .DyeIII and ^{L B} And is a covalent bond, are connected in any of ionic bond, and coordinate bond.)

X ^B1 and L ^B1 in the general formula (B) each represent a group having the same meaning as X ^A1 and L ^A1 in the general formula (A), and the preferred range is also the same.
The group represented by A in the general formula (B) may be any group capable of ionic bonding or coordination bonding with DyeIII, and the group capable of ionic bonding may be either an anionic group or a cationic group. . The anionic group is preferably an anionic group having a pKa of 12 or less, such as a carboxyl group, a phospho group, a sulfo group, an acylsulfonamide group, or a sulfonimide group, more preferably a pKa of 7 or less, still more preferably 5 or less. The anionic group may form an ionic bond or a coordinate bond with Ma or a heterocyclic group in Dye, but more preferably an ionic bond with Ma.
Specific examples of preferred anionic groups are shown below, but the present invention is not limited thereto. In the anionic groups shown below, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As the cationic group represented by A in the general formula (B), a substituted or unsubstituted onium cation (for example, a substituted or unsubstituted ammonium group, pyridinium group, imidazolium group, sulfonium group, phosphonium group, etc.) Are preferable, and a substituted ammonium group is particularly preferable.
Although the specific example of the structural unit represented by general formula (B) is shown below, this invention is not limited to this.

<Structural Unit Represented by General Formula (C)>
Next, details of the structural unit represented by the general formula (C) will be described.

(In the general formula (C), L ^C1 represents a single bond or a divalent linking group. DyeIV is a linking group having a structure in which two hydrogen atoms are removed from the partial structure represented by the general formula (5). And Dye in the general formula (5) is a dye structure in which p hydrogen atoms of a dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the following general formula (M) and a metal or metal compound are removed. P represents 1 or 2. m3 represents an integer of 1 to 4. When m3 is 2 or more, L ^C1 may be the same or different.

In the general formula (C), the divalent linking group represented by L ^C1 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.

Although the specific example used suitably as a bivalent coupling group represented by L ^C1 in general formula (C) below is described, L ^C1 of the present invention is not limited to these.

  Although the specific example of the structural unit represented by general formula (C) is shown below, this invention is not limited to this.

<Copolymerization component>
The dye multimer of the present invention may be formed of only the structural units represented by the general formula (A), the general formula (B), and the general formula (C). It may be quantified. The other structural units are preferably the structural units shown below, and specific examples thereof are shown, but the present invention is not limited thereto.

Moreover, you may have the structural unit which has a polymeric group as another structural unit. Examples of the structural unit having a polymerizable group include the following structural units.
That is, a polymerizable compound (for example, glycidyl methacrylate, methacryloxyethyl isocyanate) having a group that reacts with the structural unit in a structural unit derived from the above-described copolymer component (for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, etc.). Etc.).

  The polymerizable group contained in the structural unit having the polymerizable group (hereinafter sometimes referred to as “polymerizable unit”) is not particularly limited, and includes, for example, an ethylenically unsaturated group (for example, methacryl group, acrylic group). , Styryl groups, etc.), cyclic ether groups (for example, epoxy groups, oxetanyl groups, etc.). Among these, an ethylenically unsaturated group is preferable in terms of heat resistance and solvent resistance.

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

<Dye Multimer Represented by General Formula (D)>
Next, the details of the dye multimer represented by formula (D) will be described.

(In General Formula (D), L ^D1 represents an m4-valent linking group, and m4 represents an integer of 2 to 100. When m4 is 2 or more, the structures of DyeV may be the same or different. DyeV is a linking group having a structure in which one hydrogen atom is removed from the partial structure represented by the general formula (5), and Dye in the general formula (5) is represented by the following general formula (M). (A dye structure in which p hydrogen atoms have been removed from a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. P represents 1 or 2.)

In said general formula (D), m4 becomes like this. Preferably it is 2-80, More preferably, it is 2-40, Most preferably, it is 2-10.
In the general formula (D), when m4 is 2, the divalent linking group represented by L ^D1 is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, 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.

The m4-valent linking group having m4 of 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 using a heterocyclic linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.
Although the specific example of the pigment | dye multimer represented by general formula (D) below is shown, this invention is not limited to this.

  Hereinafter, preferred examples of the dye multimer of the present invention are shown in Tables 4 and 5 below, clearly showing the type and mass% of the structural unit (the structural unit), the weight average molecular weight, and the degree of dispersion.

The dye multimer of the present invention preferably contains a structural unit represented by the general formula (A), the general formula (B), or the general formula (C). Among these, the general formula (A) It is preferable that the structural unit represented by these is included.
Furthermore, the structural unit represented by the general formula (A) is preferably formed using a dye monomer represented by the following general formula (1) as a polymerization component.
Below, the detail about the pigment | dye monomer represented by General formula (1) is described.

<Dye monomer represented by general formula (1)>
The dye monomer contained as a polymerization component in the dye multimer of the present invention will be described in detail.
The dye monomer is a compound represented by the following general formula (1).

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound having a structure in which two hydrogen atoms are removed from the partial structure, and wherein Dye in the general formula (5) is represented by the following general formula (7) or (8): A dye structure in which p hydrogen atoms have been removed from the dipyrromethene metal complex compound obtained from 1. p represents 1 or 2. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

In the general formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ¹ represents a group that can be bonded to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other with Ma to form a 5-, 6-, or 7-member. The ring may be formed. However, R ⁴ and R ⁹ are not bonded to each other to form a ring.
In addition, the dipyrromethene metal complex compound represented by the general formula (7) includes a tautomer.

In general formula (8), R ¹¹ and R ¹⁶ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. To express. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent. R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. R ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or A 7-membered ring may be formed. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2.
In addition, the dipyrromethene metal complex compound represented by the general formula (8) includes a tautomer.

That is, the dye monomer represented by the general formula (1) is added to the dipyrromethene metal complex compound represented by the general formula (7) or the general formula (8) in the general formula (1). Q ² ) n 2-(Q ¹ ) n 1 -C (R ²¹ ) ═A compound in which a polymerizable group represented by CH ₂ is introduced.
Note that if none of n1 and n2 is 0, the above dipyrromethene metal complex compound, directly ^{-C (R} 21) = CH ₂ group is introduced. ^Here, Q 1, ^{Q 2} and ^{R 21} are the same meaning as ^Q 1, ^{Q 2} and ^{R 21} in the general formula (1).

In the dipyrromethene metal complex compound represented by the general formula (7), the site into which the polymerizable group is introduced is not particularly limited, but any one of R ^{4 to} R ⁹ is included in terms of synthesis compatibility. It is preferable that the polymerizable group is introduced into any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ , and it is more preferable that any one of R ⁴ and R ⁹ is introduced. More preferably, the polymerizable group is introduced into one of them.

In the dipyrromethene metal complex compound represented by the general formula (8), the site into which the polymerizable group is introduced is any one of R ^{11 to} R ¹⁷ , X ¹ , and Y ^{1 to} Y ² . Among these substituents, from the viewpoint of synthesis compatibility, the polymerizable group is preferably introduced into any ^one of R ^{11 to} R ¹⁶ and X ^1. R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ It is more preferable that the polymerizable group is introduced into any one of the above, and it is more preferable that the polymerizable group is introduced into any one of R ¹¹ and R ¹⁶ .

In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. When R ²¹ is an alkyl group or an aryl group, it may be unsubstituted or substituted.

When R ²¹ is an alkyl group, a substituted or unsubstituted alkyl group having 1 to 36 carbon atoms, more preferably 1 to 6 carbon atoms is preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, octyl group, isopropyl group, cyclohexyl group and the like.
When R ²¹ is an aryl group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 12 carbon atoms is preferable. Examples of the aryl group include a phenyl group and a naphthyl group.

When R ²¹ is a substituted alkyl group or a substituted aryl group, the substituent is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (preferably having 1 to 24 carbon atoms, more preferably An alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl), aryl group (preferably having 6 carbon atoms) To 24, more preferably an aryl group having 6 to 12 carbon atoms, such as phenyl, naphthyl), a heterocyclic group (preferably 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl , 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, for example, trimethylsilyl, triethylsilyl, tributyl Silyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, sulfonic acid group, phosphonic acid group, carboxyl group, alkoxy group (preferably having 1 to 24 carbon atoms, more preferably carbon An alkoxy group having 1 to 12, more preferably 1 to 6 carbon atoms, for example, a methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy group, for example, Cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferred Is an aryloxy group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenoxy or 1-naphthoxy, and a heterocyclic oxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 12 heterocyclic oxy groups such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

A silyloxy group (preferably a silyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably having 2 carbon atoms) To 24, more preferably an acyloxy group having 2 to 12 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 24 carbon atoms, more preferably 2 to 2 carbon atoms). 12, more preferably an alkoxycarbonyloxy group having 2 to 6 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyloxy)), aryloxy Carbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonyloxy), carbamoyloxy group (preferably having 1 to 24 carbon atoms, more preferably A carbamoyloxy group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyl Oxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, for example, N, N-diethylsulfuryl group. Famoyloxy, N-propylsulfamoyloxy), alkylsulfoni An oxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy) An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 12 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 24 carbon atoms, more preferably An acyl group having 1 to 12 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl),

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl ), An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 12 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 24 carbon atoms, more preferably A carbamoyl group having 1 to 12 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl − -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 24 or less carbon atoms, more preferably 12 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, Tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably an anilino group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as anilino, N-methylanilino), heterocyclic amino A group (preferably a C1-C24, more preferably a C1-C12 heterocyclic amino group such as 4-pyridylamino), a carbonamido group (preferably C2-C24, more preferably C2 ~ 12 carbonamido groups such as acetamide, benzamide, tetradecanamide, (Roylamide, cyclohexaneamide), ureido group (preferably a ureido group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide group ( Preferably, it is an imide group having 20 or less carbon atoms, more preferably 12 or less carbon atoms, for example, N-succinimide, N-phthalimide), alkoxycarbonylamino group (preferably having 2 to 24 carbon atoms, more preferably 2 carbon atoms). -12 alkoxycarbonylamino groups, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms, for example, phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 24 carbon atoms, more Preferably a sulfonamide group having 1 to 12 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 to 24 carbon atoms, More preferably, it is a sulfamoylamino group having 1 to 12 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1 to 1 carbon atoms). 24, more preferably an azo group having 1 to 24 carbon atoms , For example, phenylazo, 3-pyrazolylazo), an alkylthio group (preferably an alkylthio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group ( Preferably an arylthio group having 6 to 24 carbon atoms, more preferably an arylthio group having 6 to 12 carbon atoms, for example, phenylthio), a heterocyclic thio group (preferably having 1 to 24 carbon atoms, more preferably a heterocyclic ring having 1 to 12 carbon atoms). A thio group, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). , For example, dodecanesulfinyl),

An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 24 carbon atoms, more preferably an arylsulfinyl group having 6 to 12 carbon atoms, for example, phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 carbon atom) -12 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 carbon atoms) To 24, more preferably an arylsulfonyl group having 6 to 12 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably having 24 or less carbon atoms, more preferably carbon 16 or less sulfamoyl groups, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), A sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 24 carbon atoms, more preferably a phosphonyl group having 1 to 12 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably Is a phosphinoylamino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include diethoxyphosphinoylamino and dioctyloxyphosphinoylamino).

  Among the above substituents, halogen atom, alkyl group, aryl group, hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy group, cycloalkylcarbonyloxy group, aryl Oxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamido group, imide group, sulfonamido group , Sulfamoylamino group, sulfamoyl group are preferable, alkyl group, aryl group, hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy , Aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamido group, sulfonamido group, A sulfamoylamino group and a sulfamoyl group are more preferable, and a hydroxyl group, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfo group. More preferred are a famoyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyl group, a carbamoyloxy group, a sulfamoylamino group, an alkylsulfonyloxy group, an acyl group, an alkoxycarbonyl group is particularly preferred.

  Among the above particularly preferred substituents, a sulfonic acid group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyloxy group, an alkylsulfonyloxy group, and an alkoxycarbonyl group are more preferable, and a sulfonic acid group, a carboxylic acid group, an alkoxy group, and an alkoxycarbonyl group. A group is more preferable, and a sulfonic acid group, a carboxylic acid group, and an alkoxy group are particularly preferable.

R ²¹ is preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group.

When the substituents of the substituted alkyl group and the substituted aryl group of R ²¹ are further substitutable groups, they may be substituted with the substituents described above, and may be substituted with two or more substituents. The substituents may be the same or different.

In the general formula (1), Q ¹ represents —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) O—, a group represented by the general formula (2), a group represented by the general formula (3), or a group represented by the general formula (4). Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

R ² represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group are the alkyl groups described for the substituted alkyl group and the substituted aryl group in R ²¹ . And aryl groups are mentioned as examples, and preferred embodiments are also the same.
The alkyl group, aryl group, and heterocyclic group as R ² may be substituted with the substituent described in the above R ²¹ , and when substituted with two or more substituents, The substituents may be the same or different.

Hereinafter, as Q ¹ in the general formula (1), a group represented by the following general formula (2), a group represented by the general formula (3), and a group represented by the general formula (4) explain.

In General Formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R ²³ represents a hydrogen atom or a substituent, and k is 0 to 4 Represents an integer. When k is 2 or more, R ²³ may be the same or different. * Represents the position bonded to the —C (R ²¹ ) ═CH ₂ group in the general formula (1), and ** represents Q ² or DyeVI (when n2 = 0) in the general formula (1). Represents the position to join.

R ²² in the general formulas (3) to (4) has the same meaning as R ² described in the general formula (1), and the preferred embodiments are also the same.

R ²³ in the general formulas (2) to (4) represents a hydrogen atom or a substituent. Examples of the substituent represented by R ²³ include a substituted alkyl group and a substituted aryl group of R ²¹ in the general formula (1). The substituents described in the above are exemplified, and preferred embodiments are also the same. k represents an integer of 0 to 4, and when k is 2 or more, R ²³ may be the same or different.
When the substituent of R ^{23 in} the general formulas (2) to (4) is a further substitutable group, it may be substituted with the substituent described for R ²¹ in the general formula (1). When substituted with two or more substituents, the substituents may be the same or different.

As Q ¹ in the general formula (1), from the viewpoint of synthesis, —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) — , —C (═O) O— is preferred, —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O— are more preferred, and —C (═O ) N (R ² ) — and —C (═O) O— are more preferred. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (1), when n1 = 0, Q ² represents a divalent linking group for linking the —C (R ²¹ ) ═CH ₂ group and Dye.
Q ² is preferably an alkylene group, an aralkylene group, an arylene group, —O—, —C (═O) —, —OC (═O) —, OC (═O) O—, —OSO ₂ —, —. ^{OC (= O) N (R} 50) -, - N (R 50) -, - N (R 50) C (= O) -, - N (R 50) C (= O) O -, - N ( ^{R 50) C (= O)} N (R 51) -, - N (R 50) SO 2 -, - N (R 50) SO 2 N (R 51) -, - S -, - S-S-, _{-SO -, - SO 2 -,} - SO 2 N (R 50) -, - SO 2 O- and the like. In addition, a plurality of the above divalent linking groups may be bonded to form a new divalent linking group.

Here, R ⁵⁰ and R ⁵¹ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Preferred examples of the alkyl group, aryl group, and heterocyclic group in R ⁵⁰ and R ⁵¹ include the alkyl group, aryl group, and heterocyclic group described in the substituent of R ²¹ in formula (1). Is the same. The alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ may be substituted with the substituent described for the substituent of R ²¹ in the general formula (1), and may be substituted with two or more substituents. The substituents may be the same or different.

When Q ² in the general formula (1) is an alkylene group, an aralkylene group, or an arylene group, it may be unsubstituted or substituted, and in the case that it is substituted, it is explained by the substituent of R ^1. In the case where it is substituted with two or more substituents, these substituents may be the same or different.
When Q ² is an alkylene group, an aralkylene group, or an arylene group, an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, or an arylene group having 6 to 18 carbon atoms is preferable, and 1 to 8 carbon atoms is preferable. Are more preferable, an alkylene group having 6 to 16 carbon atoms, and an arylene group having 6 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms and an aralkylene group having 6 to 12 carbon atoms.

As a combination of Q ¹ and Q ² , Q ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) a O-, ^{Q 2} is an alkylene group having 1 to 12 carbon atoms, an aralkylene group of 6 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, alkyl thioether having 2 to 18 carbon atoms, carbon atoms 2 Preferred are an alkylcarbonamide group having ˜18 and an alkylaminocarbonyl group having 2 to 18 carbon atoms. More preferably, Q ¹ is —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O—, and Q ² is an alkylene group having 1 to 8 carbon atoms, Embodiments of an aralkylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an alkylthioether having 2 to 12 carbon atoms, an alkylcarbonamide group having 2 to 12 carbon atoms, and an alkylaminocarbonyl group having 2 to 12 carbon atoms And more preferably, Q ¹ is —C (═O) N (R ² ) —, —C (═O) O—, Q ² is an alkylene group having 1 to 6 carbon atoms, and 6 to 12 carbon atoms. Are an aralkylene group, an alkylthioether having 2 to 6 carbon atoms, an alkylcarbonamide group having 2 to 6 carbon atoms, and an alkylaminocarbonyl group having 2 to 6 carbon atoms.

Below, in the general formula (1) in ^{- (Q 2) n2- (Q} 1) n1-C (R 21) = Examples of the polymerizable group represented by CH _2. However, the present invention is not limited to these.

(Dipyrromethene metal complex compound)
The dye monomer represented by the general formula (1) is a dye residue obtained by removing one arbitrary hydrogen atom from the dipyrromethene metal complex compound represented by the general formula (7), or the general formula (8). ) Of the dipyrromethene metal complex compound represented by the formula (1) has a dye residue in which one hydrogen atom of any one of R ^{11 to} R ¹⁹ and X ³ is removed. In other words, the dye monomer represented by the general formula (1) is added to the dipyrromethene metal complex compound represented by the general formula (7) or the general formula (8) to-(Q ² ) n2- ( Q ¹ ) A compound in which a polymerizable group represented by n ¹ -C (R ²¹ ) ═CH ₂ is introduced. Note that if none of n1 and n2 is 0, the above dipyrromethene metal complex compound, directly ^{-C (R} 21) = CH ₂ group is introduced.
The dipyrromethene metal complex compound introduced into the general formula (1) is a dipyrromethene metal complex compound represented by the general formula (7) or the general formula (8) described in detail above.

The dye monomer represented by the general formula (1) contained in the dye multimer of the present invention may be one kind or two or more kinds.
Further, the dye multimer of the present invention contains a monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond as a copolymer component. May be. In this case, the said monomer may contain only 1 type and may contain 2 or more types. In addition, other monomers that may be further included as a copolymerization component may include only one type or two or more types when they are included as a copolymerization component. .
A monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond will be described later.

The dye multimer of the present invention can form a structural unit represented by the general formula (A), the general formula (B), and the general formula (C) or a structural unit represented by the general formula (A). What contains the pigment | dye monomer represented by General formula (1) which is a preferable monomer by 100 mass% by mass ratio (mass%), ie, general formula (A), general formula (B), and general A multimer obtained by polymerizing only the structural unit represented by the formula (C) may be used.
From the viewpoint of coloring power, the dye multimer of the present invention has a constitutional unit represented by general formula (A), general formula (B), and general formula (C) in a mass ratio (mass%) of 10 It is preferable to contain from mass% to 100 mass%, more preferably from 20 mass% to 100 mass%, and even more preferably from 30 mass% to 100 mass%.

<Monomer having a different structure from the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond>
The dye multimer of the present invention is represented by the general formula (A), the general formula (B) and the structural unit represented by the general formula (C) as a polymerization component, and the general formula (1) which is a preferred embodiment thereof. In addition, a monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond (hereinafter referred to as appropriate) "Other ethylenically unsaturated bond monomers"). Furthermore, a monomer having a structure different from that of other ethylenically unsaturated bond monomers may be included as a copolymerization component.
That is, the dye multimer of the present invention comprises a dye monomer capable of forming a structural unit represented by the general formula (A), the general formula (B), and the general formula (C), the general formula (1). And a copolymer containing other ethylenically unsaturated bond monomers. At this time, the copolymer may contain only one type of the specific dye monomer according to the present invention, or may contain two or more types, and the other ethylenically unsaturated bond monomer. 1 type may be included and 2 or more types may be included.

The other ethylenically unsaturated bond monomer is a compound having an ethylenically unsaturated bond at least at a terminal portion, and is represented by the general formula (A), the general formula (B), and the general formula (C). The dye monomer capable of forming the structural unit represented and the dye monomer represented by the general formula (1) are not particularly limited as long as the monomer has a different structure.
When applying the dye multimer of the present invention to a colored curable composition, from the viewpoint of improving the color pattern forming property, other ethylenically unsaturated bond monomers are added to the terminal ethylenically unsaturated bond, A monomer having an alkali-soluble group is preferable.

Examples of the other ethylenically unsaturated bond monomer having an alkali-soluble group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a monomer having a phosphate group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-poly Caprolactone mono (meth) acrylate can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  The dye multimer of the present invention preferably contains a repeating unit derived from a vinyl monomer having an alkali-soluble group as described above. By including such a repeating unit, when the dye multimer of the present invention is applied to a colored curable composition, the development removability of an unexposed portion is excellent.

In the dye multimer of the present invention, the content of the repeating unit derived from the vinyl monomer having an alkali-soluble group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mgKOH / g as the acid value of the dye multimer. g. By being this range, the production | generation of the deposit in a developing solution is suppressed.
Further, when the colored curable composition is constituted by using the dye multimer of the present invention and the pigment together with the acid value in the above-mentioned range, the secondary aggregate is an aggregate of primary particles of the pigment. Can be effectively suppressed, or the cohesive force of the secondary aggregate can be effectively weakened.

  The vinyl monomer that can be used in the copolymerization with the dye monomer of the present invention is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumarate Acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Specific examples of other ethylenically unsaturated bond monomers that can be used in the present invention are shown below, but the present invention is not limited thereto.

  Further, the dye compound of the present invention may contain a polymerizable group introduced by adding a compound having a polymerizable group and a group that reacts with a substituent contained in the dye compound to the dye compound.

Examples of the group that reacts with a substituent contained in the dye compound include a monovalent leaving group (for example, a chlorine atom, a bromine atom, an iodine atom, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and 4 to 4 carbon atoms). 9 cycloalkylcarbonyloxy groups, arylcarbonyloxy groups having 7 to 12 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 5 carbon atoms, triflates, etc.), acid groups (for example, carboxylic acids, sulfonic acids, phosphoric acids, etc.) ), Hydroxyl groups, primary and secondary amino groups, and the like. For example, the group that reacts with the hydroxyl group of the dye compound may be an epoxy group or a monovalent leaving group (for example, Valent leaving group), isocyanate groups, and the like. Examples of groups that react with chlorine atoms of dye compounds include thiol groups, hydroxyl groups, primary and secondary amino groups, and carbonyl groups. Etc., and the like. Moreover, as a polymeric group, an ethylenically unsaturated group, an epoxy ring, an oxetane ring etc. are mentioned.
Examples of the compound having a polymerizable group and a group that reacts with a substituent contained in the dye compound include glycidyl (meth) acrylate, allyl bromide, paravinylphenyl bromide, methacryloxyethyl isocyanate, and preferably glycidyl. (Meth) acrylate and methacryloxyethyl isocyanate.

Examples of the dye compound having a polymerizable group introduced by adding a compound having a group capable of reacting with a substituent contained in the dye compound and a polymerizable group to the dye compound include the following. .
The dye compound having a polymerizable group may contain a dye compound before introducing the polymerizable group.

(Specific examples of dye multimers)
Specific examples of the dye multimer of the present invention are shown below, but the present invention is not limited thereto. In the table, the number of monomer a corresponds to the specific example of the dye monomer described above, and the number of monomer b corresponds to the specific example of the ethylenically unsaturated bond monomer described above. Correspond.

  In addition, as a manufacturing method of a pigment | dye multimer, the pigment | dye multimer which comprises the structural unit derived from the pigment | dye monomer represented by the said General formula (1) is represented independently or by General formula (1). Including a dye multimer comprising a structural unit derived from a dye monomer and the above-described ethylenically unsaturated bond monomer, and can be synthesized by radical polymerization, photoradical polymerization, thermal polymerization, Radical polymerization is preferred.

The molecular weight of the dye multimer of the present invention is preferably in the range of 5000 to 30000 in terms of weight average molecular weight (Mw) and in the range of 3000 to 20000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 5000 to 25000, and the number average molecular weight (Mn) is in the range of 3000 to 17000. Particularly preferably, the weight average molecular weight (Mw) is in the range of 5000 to 20000, and the number average molecular weight (Mn) is in the range of 3000 to 15000.
From the viewpoint of developability when the color multimer of the present invention is applied to a colored curable composition to produce a color filter, the weight average molecular weight (Mw) of the specific polymer is preferably 20000 or less.

(Method for producing dipyrromethene metal complex compound)
The manufacturing method of the dipyrromethene metal complex compound of this invention is described.

(Complexation reaction)
The dipyrromethene metal complex compound of the present invention is represented by the following general formula (I) by reacting a dipyrromethene compound represented by the following general formula (XI) with a metal derivative represented by the following general formula (XIII). The obtained dipyrromethene metal complex compound can be obtained (hereinafter, this reaction is referred to as “complexation reaction”).

(In General Formula (I), G ⁴ and G ⁶ each independently represent a monovalent substituent having a steric parameter of -Es ′ value of 1.5 or more. R ³² , R ³³ , R ³⁵ , and R ³⁶ each independently represent a hydrogen atom, or ^{.R 37} representing a monovalent substituent include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic represents a group ^{.R 31, R 34} are each independently hydrogen Represents an atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, Ma represents a metal atom or a metal compound, and X ³ represents a group capable of bonding to Ma. And a represents 0, 1, or 2.)

(In the general formula ^{(XI), R} 31 ~R ³⁷ and ^G 4, ^{G 6} are the same respectively ^R 31 ^{to R 37} and ^G 4, ^{G 6} in the general formula (I).)

(In the general formula (XIII), Ma, and ^{X 1} .b respectively synonymous Ma, and ^{X 3} and in the formula (I) represents an integer of 0 to 4.)

In the dipyrromethene metal complex compound represented by the above general formula (I), R ³² , R ³³ , R ³⁵ and R ³⁶ are respectively synonymous with R ⁵ , R ⁶ , R ⁸ and R ⁷ in the general formula (M). There are also preferred embodiments. R ³⁷ has the same meaning as R ¹⁰ in formula (M), and a preferred embodiment is also the same. Ma is synonymous with Ma in the said General formula (7), and its preferable range is also the same. R ³¹ , R ³⁴ , and X ³ have the same meanings as R ¹⁸ , R ¹⁹ , and X ³ in the general formula (8), respectively, and preferred ranges thereof are also the same.

More specifically, in the general formula (I), among R ³² , R ³³ , R ³⁵ and R ³⁶ , R ³² and R ³⁵ are each an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group. Group, arylsulfonyl group, nitrile group, imide group or carbamoylsulfonyl group is preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferable, alkoxy A carbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
R ³³ and R ³⁶ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted An unsubstituted aryl group. Here, specific examples of more preferable alkyl groups, aryl groups, and heterocyclic groups can similarly include specific examples listed in R ⁶ and R ⁷ in the general formula (M).

Among these, R ³¹ and R ³⁴ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In the general formula (I), G ⁴ and G ⁶ each independently represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. Specifically, an alkyl group (preferably a branched chain having 1 to 36 carbon atoms, more preferably a branched chain having 1 to 12 carbon atoms, or a cyclic alkyl group, for example, a substituent 2-ethylhexyl group, 1 -Adamantyl group, triethylmethyl group), alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, vinyl group, allyl group, 3-buten-1-yl group) An aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, for example, a phenyl group, an o-tolyl group, a naphthyl group), a heterocyclic group (preferably having 1 to 24 carbon atoms). More preferably, it is a heterocyclic group having 1 to 12 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2-pyridyl group, 2-benzothiazolyl. Represents 1-imidazolyl, 1-pyrazolyl group, a benzotriazol-1-yl group).

Among these, G ⁴ and G ⁶ are preferably an alkyl group, an alkenyl group, and an aryl group, more preferably an alkyl group and an alkenyl group, and particularly preferably an alkyl group.

In the general formula (8), examples of the group capable of binding to Ma represented by X ³ include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a “metal chelate” ([1] Sakaguchi Takeichi and Ueno Keihei (1995 Nanedo), [2] (1996), [3] (1997), etc.). Among these, from the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a halogen atom, a hydroxyl group, and a carboxylic acid group are more preferable. a represents 0, 1, or 2. When a is 2, the structures of X ³ may be the same or different.

In general formula (I), R ³¹ and G ⁴ are bonded to each other to form a 5-membered ring together with carbon atoms (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (I), R ³⁴ and G ⁶ are bonded to each other to form a 5-membered ring together with carbon atoms (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In general formula (I), G ⁴ and G ⁶ are each independently a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. G ⁴ and G ⁶ are each independently more preferably 2.0 or more, further preferably 3.5 or more, and particularly preferably 5.0 or more.

As a preferable aspect of the compound represented by the general formula (I), R ³² , R ³³ , R ³⁵ , and R ³⁶ are each independently R ⁵ , R ⁶ , R ⁸ , R ⁷ is a preferred embodiment described in the description of R ⁷ , R ³⁷ is a preferable embodiment described in the description of R ¹⁰ in the general formula (M), and R ³¹ and R ³⁴ are each independently a hydrogen atom or an alkyl group. Each of G ⁴ and G ⁶ independently represents an alkyl group, an alkenyl group, or an aryl group having an -Es ′ value of 2.0 or more, Ma represents Zn, Cu, Co, or V═O, and X ¹ is a group bonded through an oxygen atom, and a is 0 or 1.

As a more preferable embodiment of the compound represented by the general formula (I), R ³² , R ³³ , R ³⁵ and R ³⁶ are each independently R ⁵ , R ⁶ , R ⁸ and R ⁷ in the general formula (M). R ³⁷ is a preferable embodiment described in the description of R ¹⁰ in the general formula (M), R ³¹ and R ³⁴ are each independently a hydrogen atom or an alkyl group, G ⁴ and G ⁶ are each independently an alkyl group or alkenyl group having an -Es ′ value of 3.5 or more, Ma is Zn, X ³ is a group bonded through an oxygen atom, and a is 0 or 1.

The site for introducing an formula dipyrromethene metal complex compound of formula (I) to the dye multimer will be described later, but unless not particularly limited to impair the effects of the present ^{invention, R 31 ~R 36, X 3} , G 4, it is preferably one of G ^6. Among these, it is preferable to introduce | transduce in any one of R ^{< 32>} , R ^<33> , R ^<35> , R ^<36> , X < ³ >, G < ⁴ >, and G < ⁶ > from the point of synthetic compatibility, More preferably, R ³² , R ³⁵ , X ³ , G ⁴ , and G ⁶ are inserted in any one of the embodiments, and more preferably G ⁴ and G ⁶ are inserted in any one of them.

As a method for introducing an alkali-soluble group into the dye compound of the present invention, when a dye monomer or structural unit having an alkali-soluble group is used, R ^{31 to} R of the dipyrromethene metal complex compound represented by the general formula (I) are used. Any one or two or more substituents of ³⁷ , X ³ , G ⁴ and G ⁶ may contain an alkali-soluble group. Among these substituents, any of R ³² , R ³³ , R ³⁵ , R ³⁶ , X ³ , G ⁴ , and G ⁶ is preferable, and any of R ³² , R ³⁵ , G ⁴ , and G ⁶ is preferred. Preferably, any of G ⁴ and G ⁶ is more preferable.

  The dipyrromethene metal complex compound represented by the general formula (I) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.

  The organic solvent used in the complexing reaction is not particularly limited, but it is preferably performed in a protic polar solvent or an aprotic polar solvent from the viewpoint of solubility in the metal derivative represented by the general formula (XIII). In particular, alcohol organic solvents (methanol, ethanol, isopropyl alcohol, etc.), ether solvents (tetrahydrofuran, dioxane, cyclopentyl methyl ether, etc.), acetone, acetonitrile, N, N-dimethylformamide, or N-methyl-2-pyrrolidone A polar solvent such as is mentioned as a suitable solvent. These may be used alone or in combination of two or more.

The reaction temperature of the complexing reaction is 0 ° C. or higher, and can be selected in the temperature range of the boiling point temperature or lower of the solvent used according to the raw materials used.
In addition, the charged molar ratio between the dipyrromethene compound represented by the general formula (XI) and the metal derivative represented by the general formula (XIII) is the dipyrromethene compound represented by the general formula (XI): general formula (XIII) Is preferably 1:10 to 10: 1, more preferably 1: 3 to 3: 1, and further preferably 1.2: 1 to 1: 1.2. A ratio of 1: 1 is particularly preferable.

(Coupling reaction A)
A dipyrromethene compound represented by the general formula (XI) can be obtained by reacting a substituted pyrrole compound represented by the following general formula (V) with a substituted pyrrole compound represented by the following general formula (X). (This reaction is hereinafter referred to as “coupling reaction A”).

In the general formula ^{(V), R 31, R} 32, R 33, and ^{G 4} are each the same meaning as ^{R 31, R 32, R 33} , G 4 in formula (I), preferable embodiments thereof are also the same .

In the general formula ^{(X), R 34, R} 35, R 36, R 37, and ^{G 6} is, ^R 34 in the general formula ^{(I), R 35, R} 36, R 37, and ^{G 6} and have the same meanings The preferred embodiment is also the same.

  Coupling reaction A is described, for example, in Aust. J. et al. Chem, 1965, 11, 1835-45, U.S. Pat. No. 4,774,339, JP-A-2008-292970, and JP-A-2009-227639.

  The coupling reaction A is preferably performed in the presence of an acid from the viewpoint of synthesis applicability. Specific examples include hydrobromic acid, hydrochloric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic acid and the like. Moreover, although there is no restriction | limiting in particular in the quantity which uses an acid, it is preferable to use 1-200 equivalent with respect to the substituted pyrrole compound represented by general formula (X), and it is more preferable to use 1-10 equivalent. Moreover, you may use an acid as a solvent.

  In the coupling reaction A, a dehydrating agent may be used from the viewpoint of synthesis applicability. Specific examples include acid anhydrides (such as acetic anhydride, trifluoroacetic anhydride, and trifluoromethanesulfonic acid anhydride), trimethylsilyl chloride, and phosphorus oxychloride. Moreover, there is no restriction | limiting in particular in the quantity which uses a dehydrating agent, However, It is preferable to use 1-200 equivalent with respect to the substituted pyrrole compound represented by general formula (X). Further, the dehydrating agent may be used as a solvent.

  The organic solvent used in the coupling reaction A is not particularly limited as long as the reaction is not inhibited. When the reaction is performed in the presence of an acid, a solvent that does not react with an acid is preferable, and a halogen-based solvent (dichloromethane and the like), toluene, acetonitrile, and an alcohol-based solvent (methanol, ethanol, isopropyl alcohol, and the like) are preferable. Moreover, you may use said acid and dehydrating agent which are reactants as a solvent. These may be used alone or in combination of two or more.

The reaction temperature of the coupling reaction A can be selected in the temperature range of −50 ° C. to 200 ° C. according to the raw material used, but the temperature range of −10 ° C. to 150 ° C. is preferable, and 0 ° C. to 100 ° C. A temperature range of ° C is more preferred.
The charged molar ratio between the substituted pyrrole compound represented by the general formula (V) and the substituted pyrrole compound represented by the general formula (X) is the substituted pyrrole compound represented by the general formula (V): The substituted pyrrole compound represented by X) is preferably 1:10 to 10: 1, more preferably 1: 3 to 3: 1, and 1.2: 1 to 1: 1.2. More preferably, the ratio is 1: 1.

(Acylation reaction)
By reacting a compound represented by the following general formula (IX) with an acylating agent (including a formylating agent), a compound represented by the above general formula (X) can be obtained, and using this compound, dipyrromethene is used. A compound can be obtained.

In the general formula ^{(IX), R 34, R} 35, R 36, and ^{G 6 is, R 34, R 35, R} 36 in the general formula (I), and ^{G 6} and have the same meanings, a preferred embodiment also the same is there.

  Regarding the acylation reaction of pyrrole, for example, the literature (Hiroshi Yamanaka, Atsushi Hino, Masako Nakagawa, Naoko Sakamoto, New edition of heterocyclic compounds, published on March 1, 2004 (Kodansha Scientific, Chapter 1, 31-31) 32) can be used, that is, Gattermann reaction, Vilsmeier reaction, Houben-Hosch reaction, Friedel-Crafts reaction, etc. Among them, from the viewpoint of production applicability, It is preferable to use a Vilsmeier reaction or a Friedel-Crafts reaction.

(Vilsmeier reaction)
Regarding the Vilsmeier reaction of pyrrole, for example, a known method shown in the literature (Jones, G., Stanforth, SP The Vilsmeier reaction of fully conjugated carbocycles and heterocycles. Org. React. 1997, 49, 1-330.) Is used. Can be used. An example in which the Vilsmeier reaction is applied to synthesize a dipyrromethene metal complex compound is described in, for example, JP-A-2001-240761.

  In the Vilsmeier reaction, a Vilsmeier reactant is prepared from an N, N-disubstituted amide and an acid chloride, but generally suitable reactants can be used. Specifically, examples of N, N-disubstituted amides include N, N-dimethylformamide, N-methylformanilide, acetanilide and the like. Examples of the acid chloride include phosphorus oxychloride, thionyl chloride, oxalyl chloride, 2,4,6-trichloro-1,3,5-triazine and the like.

  The organic solvent used in the Vilsmeier reaction is not particularly limited as long as it does not inhibit the reaction, but a solvent that does not react with an acid is preferable, and halogen solvents (dichloromethane and the like), toluene, acetonitrile, phosphorus oxychloride, N, N-dimethylformamide, and the like are preferable. Mentioned as suitable solvents. These may be used alone or in combination of two or more.

The reaction temperature of the Vilsmeier reaction can be selected in the temperature range of −50 ° C. to 200 ° C. according to the raw material used, but the temperature range of 0 ° C. to 100 ° C. is preferable, and the temperature of 10 ° C. to 60 ° C. A range is more preferred.
The charged molar ratio of the Vilsmeier reactant to the substituted pyrrole compound represented by the general formula (IX) is 1 to 10 times the substituted pyrrole compound represented by the general formula (IX): Vilsmeier reactant = 1 to 10 times. Preferably, it is 1 to 5 times, more preferably 1 to 2 times.

(Friedel-Crafts reaction)
Regarding the Friedel-Crafts reaction of pyrrole, for example, literature (Hiroshi Yamanaka, Atsushi Hino, Masako Nakagawa, Naoko Sakamoto, new edition, Basics of heterocyclic compounds, published on March 1, 2004 (Kodansha Scientific, Chapters 31, 31-31) The known method shown on page 32) can be used.

In the Friedel-Crafts reaction, an acylating agent represented by the following general formula (XV) is used. Here, in the general formula ^{(XV), R 37} has the same meaning as ^{R 37} in formula (I), preferable embodiments thereof are also the same. X represents a leaving group. Specifically, it is a chlorine atom, a bromine atom, an iodine atom, a triflate, etc., and a chlorine atom is preferable from the viewpoint of production adaptability.

  As the Lewis acid catalyst used in the Friedel-Crafts reaction, a Lewis acid catalyst generally used as a suitable catalyst can be used. Specific examples include aluminum chloride, aluminum bromide, lanthanoid triflate, sulfuric acid, phosphoric acid, iron trichloride, zinc dichloride, and polyphosphoric acid. These may be used alone or in combination of two or more.

  The organic solvent used in the Friedel-Crafts reaction is not particularly limited as long as the reaction is not inhibited, but a halogen-based solvent (dichloromethane and the like), nitrobenzene and the like can be mentioned as suitable solvents. These may be used alone or in combination of two or more.

  The reaction temperature of the Friedel-Crafts reaction can be selected in the temperature range of −50 ° C. to 200 ° C. according to the raw materials used, but the temperature range of −10 ° C. to 100 ° C. is preferable, and 0 ° C. to 60 ° C. A temperature range of ° C is more preferred.

  The charged molar ratio of the acylating agent represented by the general formula (XV) to the substituted pyrrole compound represented by the general formula (IX) is the substituted pyrrole compound represented by the general formula (IX): The acylating agent represented is preferably 1 to 10 times, more preferably 1 to 5 times, and most preferably 1 to 2 times. Moreover, the charged molar ratio of the Lewis acid catalyst to the substituted pyrrole compound represented by the general formula (IX) is 1 to 10 times the substituted pyrrole compound represented by the general formula (IX): Lewis acid catalyst. Is preferably 1 to 5 times, more preferably 1 to 2 times.

(Coupling reaction B)
By reacting a compound represented by the following general formula (V), a compound represented by the following general formula (IX), and a compound represented by the following general formula (XII), the above general formula (XI) (Hereinafter, this reaction is referred to as “coupling reaction B”).

In the general formula ^{(V), R 31, R} 32, R 33, and ^{G 4, R 31, R 32, R} 33 in Formula (I), and ^{G 4} and have the same meanings, preferred embodiments as well It is.

In the general formula ^{(IX), R 34, R} 35, R 36, and ^{G 6 is, R 34, R 35, R} 36 in Formula (I), and a ^{G 6} have the same meanings, preferred embodiments as well It is.

In the general formula (XII), R ³⁷ has the same meaning as R ³⁷ in the general formula (I), and preferred embodiments thereof are also the same. ^R38 represents an alkyl group or an aryl group.

More specifically, in the general formula (XII), R ³⁸ represents an alkyl group (preferably having 1 carbon atom).
To 36, more preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl , Cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl or naphthyl).

In general formula (XII), R ³⁸ is preferably an alkyl group, and more preferably a methyl group or an ethyl group.

  Coupling reaction B can be synthesized, for example, according to the methods described in JP-A-2008-292970 and JP-A-2009-227639.

  The coupling reaction B is preferably carried out in the presence of an acid from the viewpoint of synthesis applicability. Specific examples include hydrobromic acid, hydrochloric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic acid and the like. Moreover, although there is no restriction | limiting in particular in the quantity which uses an acid, it is preferable to use 1-200 equivalent with respect to the substituted pyrrole compound represented by general formula (X), and it is more preferable to use 1-10 equivalent. Moreover, you may use an acid as a solvent.

  In the coupling reaction B, a dehydrating agent may be used from the viewpoint of synthesis applicability. Specific examples include acid anhydrides (such as acetic anhydride, trifluoroacetic anhydride, and trifluoromethanesulfonic acid anhydride), trimethylsilyl chloride, and phosphorus oxychloride. Moreover, although there is no restriction | limiting in particular in the quantity which uses a dehydrating agent, it is preferable to use 1-200 equivalent with respect to the substituted pyrrole compound represented by general formula (X), and it is more preferable to use 1-10 equivalent. Further, the dehydrating agent may be used as a solvent.

  The organic solvent used in the coupling reaction B is not particularly limited as long as the reaction is not inhibited. When the reaction is performed in the presence of an acid, a solvent that does not react with an acid is preferable, and a halogen-based solvent (dichloromethane and the like), toluene, acetonitrile, and an alcohol-based solvent (methanol, ethanol, isopropyl alcohol, and the like) are preferable. Moreover, you may use said acid and dehydrating agent which are reactants as a solvent. These may be used alone or in combination of two or more.

  The reaction temperature of the coupling reaction B can be selected in the temperature range of −50 ° C. to 200 ° C. according to the raw materials used, but the temperature range of −10 ° C. to 150 ° C. is preferable, and 0 ° C. to 100 ° C. A temperature range of ° C is more preferred.

The charged molar ratio of the substituted pyrrole compound represented by the general formula (V) and the substituted pyrrole compound represented by the general formula (IX) is the substituted pyrrole compound represented by the general formula (V): The substituted pyrrole compound represented is preferably 1:10 to 10: 1, more preferably 1: 3 to 3: 1, and further preferably 1.2: 1 to 1: 1.2. A ratio of 1: 1 is particularly preferable.
The charged molar ratio of the amount of the compound represented by the general formula (XII) to the total amount of the substituted pyrrole compounds represented by the general formula (V) and the general formula (IX) is the total amount: The amount of the compound represented by formula (XII) is preferably 0.1 times to 2.5 times, more preferably 0.3 times to 1.0 times, and more preferably 0.5 times. Most preferred.

Further, the leaving group X ¹¹ in the compound represented by the following general formula (IV), by chemically substituent conversion, to form a substituent G ⁴ in the compound represented by the general formula (V) The substituted pyrrole compound represented by the general formula (V) can be obtained.

In the general formula ^(IV), R ^31, R ^{32, R 33} are each synonymous with ^{R 31,} R ^{32, R 33} in the general formula (I). R ³⁹ and R ⁴⁰ each independently represents an alkyl group, alkenyl group, aryl group or heterocyclic group having 2 or more carbon atoms. X ¹¹ represents a monovalent leaving group. n represents 0-10.

(Amidation reaction)
The pyromethene compound includes a compound represented by the following general formula (II) and a general formula (III
The substituted pyrrole compound represented by the above general formula (IV) can be obtained by reacting with an acid halide represented by formula (IV) (hereinafter, this reaction is referred to as “amidation reaction”).

In the general formula ^(II), R ^31, R ^{32, R 33} are each synonymous with ^{R 31,} R ^{32, R 33} in the general formula (I).

In the general formula ^{(III), R 39, R} 40, X 11 and n have the same meanings as ^{R 39, R 40, X 11} and n in the general formula (IV). X ¹² represents a monovalent leaving group.

X ¹² in the general formula (III) is a chlorine atom, a bromine atom, an iodine atom, or a carbon number of 2
An alkylcarbonyloxy group having 6 to 6 carbon atoms, a cycloalkylcarbonyloxy group having 4 to 9 carbon atoms, an arylcarbonyloxy group having 7 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, a triflate, and the like. From the viewpoint of adaptability, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a chlorine atom, and a bromine atom are preferable, and a methylcarbonyloxy group and a chlorine atom are most preferable.

  The amidation reaction can be synthesized, for example, according to the method described in Fourth Edition Experimental Chemistry Lecture 22 Organic Synthesis IVp137-151.

In the amidation reaction, it is preferable to use a base as necessary. Specific examples include triethylamine, diisopropylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene. Moreover, there is no restriction | limiting in particular in the quantity which uses a base, However, It is preferable to use 0.01-5 equivalent with respect to the acid halide represented by the said general formula (III), and 0.1-3 equivalent is used. More preferred. These may be used alone or in combination of two or more.

  The organic solvent used in the amidation reaction is not particularly limited as long as the reaction is not inhibited. Suitable solvents include halogenated solvents (dichloromethane and the like), acetonitrile and the like. These may be used alone or in combination of two or more.

  The reaction temperature of the amidation reaction can be selected in the temperature range of −50 ° C. to 150 ° C. according to the raw materials used, but the temperature range of −10 ° C. to 120 ° C. is preferable, and 0 ° C. to 100 ° C. The temperature range is more preferable.

The charged molar ratio of the substituted pyrrole compound represented by the general formula (II) to the acid halide represented by the general formula (III) is the substituted pyrrole compound represented by the general formula (II):
) Represented by acid halides = 1: 10 to 10: 1, more preferably 1: 3 to 3: 1, and 1.2: 1 to 1: 1.2. Is more preferable, and 1: 1 is particularly preferable.

  A dipyrromethene metal complex compound particularly preferred in the present invention can be produced using the substituted pyrrole compound thus obtained.

(Radical polymerization reaction)
A dye multimer comprising a structural unit derived from the dye monomer represented by the following general formula (1) is synthesized by radical polymerization of the dye monomer represented by the following general formula (1). (This reaction is hereinafter referred to as “radical polymerization reaction”).

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene obtained from a dipyrromethene compound and a metal or metal compound, which is a linking group having a structure in which two hydrogen atoms are removed from a partial structure, and Dye in the general formula (5) is represented by the following general formula (M) This is a dye structure in which p hydrogen atoms have been removed from a metal complex compound, where p represents 1 or 2. R ² represents hydrogen. Represents an atom, an alkyl group, an aryl group, or a heterocyclic group.)

  The radical polymerization reaction can be synthesized, for example, according to the method described in Fourth Edition Experimental Chemistry Lecture 28 Polymer Synthesis.

In the radical polymerization reaction, it is preferable to use a radical polymerization initiator. Specifically, azo initiators (azoisobutyronitrile, dimethyl 2,2-azobisisobutyrate, dimethyl 2,2′-azobis (2-methylpropionate), etc.), peroxide initiators ( Benzoyl peroxide, di-t-butyl peroxide, etc.).
Moreover, there is no restriction | limiting in particular in the quantity which uses a radical polymerization initiator, However, It is preferable to use 0.01-0.5 equivalent with respect to the pigment | dye monomer represented by General formula (1), 0.03- More preferably, 0.3 equivalent is used. These may be used alone or in combination of two or more.

In the radical polymerization reaction, a chain transfer agent may be used from the viewpoint of reaction control. Specific examples include thiols (such as dodecanethiol and thiomalic acid), disulfides (such as diphenyl disulfide), and carbon tetrachloride.
Moreover, there is no restriction | limiting in particular in the quantity which uses a chain transfer agent, However, It is preferable to use 0.01-0.5 equivalent with respect to the pigment | dye monomer represented by General formula (1), 0.03-0 It is more preferable to use 3 equivalents. These may be used alone or in combination of two or more.

  The organic solvent used in the radical polymerization reaction is not particularly limited as long as the reaction is not inhibited. Suitable solvents include propylene glycol methyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), cyclohexanone, butyl acetate, halogenated solvents (dichloromethane, etc.), acetonitrile and the like. These may be used alone or in combination of two or more.

  The reaction temperature of the radical polymerization reaction can be selected in the temperature range of 0 ° C. to 150 ° C. according to the raw material used, but the temperature range of 30 ° C. to 120 ° C. is preferable, and the temperature of 40 ° C. to 100 ° C. A range is more preferred.

In the radical polymerization reaction, in addition to the dye monomer represented by the general formula (1), the structure is different from that of the dye monomer represented by the general formula (1) and has a terminal ethylenically unsaturated bond. A mer may be used. Specific examples of the monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond are not particularly limited, but in the present specification [0317] to Specific examples include the vinyl monomers listed in [0323].
The amount of the monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond is not particularly limited, but is represented by the general formula (1). It is preferable to use 0.1-10 equivalent with respect to the pigment | dye monomer used, and it is more preferable to use 0.2-5 equivalent. These may be used alone or in combination of two or more.

  As the polymerization method of this radical polymerization reaction, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be adopted, but solution polymerization is preferable from the viewpoint of reaction control. In addition, as a polymerization method, raw materials excluding an initiator and a polymerization catalyst are initially charged all at once, and a polymerization method in which polymerization is started by adding an initiator and a polymerization catalyst, and a dropping polymerization method in which raw materials are added dropwise over several hours. A partial dropping polymerization method in which a part of raw materials is charged in advance and the rest is added dropwise may be employed.

(Polymerizable group introduction reaction)
Homopolymerizing a dye monomer represented by the following general formula (1), or a dye monomer represented by the following general formula (1) and a dye monomer represented by the general formula (1) A multimer is obtained by copolymerization with a monomer having a different structure and having a terminal ethylenically unsaturated bond, and then a compound having a group capable of reacting with the multimer and a polymerizable group is added to the multimer. Thus, a polymerizable group-containing dye multimer that introduces a polymerizable group can be synthesized (hereinafter, this reaction is referred to as “polymerizable group introduction reaction”).

  As the polymerizable group introduction reaction, for example, a reaction in which Exemplified Compound P51 having a carboxylic acid moiety and glycidyl methacrylate are reacted in the presence of a catalyst such as an ammonium salt (hereinafter, this reaction is referred to as “GMA reaction”), a large amount. There is a method of converting a halogen group in the body into a terminal ethylenically unsaturated bond by a dehydrohalogenation reaction.

(GMA reaction)
The GMA reaction preferably uses a catalyst. Specifically, ammonium salts (tetrabutylammonium bromide, tetrabutylammonium chloride, etc.), amines (N, N-dimethyldodecylamine, diisopropylethylamine, etc.), phosphorus compounds (triphenylphosphine, etc.), betaines (trimethylglycine, etc.) Etc.).

  Moreover, there is no restriction | limiting in particular in the quantity which uses catalysts, such as an ammonium salt, It is preferable to use 0.01-0.5 equivalent with respect to the pigment | dye monomer represented by General formula (1), and 0.03 It is more preferable to use -0.3 equivalent. These may be used alone or in combination of two or more.

  The organic solvent used in the GMA reaction is not particularly limited as long as the reaction is not inhibited. Suitable solvents include propylene glycol methyl ether acetate, N-methylpyrrolidone, cyclohexanone, butyl acetate, halogenated solvents (dichloromethane and the like), acetonitrile and the like. These may be used alone or in combination of two or more.

  The reaction temperature of the GMA reaction can be selected in the temperature range of 0 ° C. to 150 ° C. according to the raw materials used, but the temperature range of 30 ° C. to 120 ° C. is preferable, and the temperature of 40 ° C. to 100 ° C. A range is more preferred.

  The substituted pyrrole compound of the present invention is a compound represented by the following general formula (V) or (X).

(In the general formula (V), R ³² and R ³³ each independently represents a hydrogen atom or a monovalent substituent. R ³¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group. Represents an alkylsulfonyl group or an arylsulfonyl group, and G ⁴ represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more.)

In the general formula ^{(V), R 31, R} 32, R 33, and ^{G 4} are each the same meaning as ^{R 31, R 32, R 33} , G 4 in formula (I), preferable embodiments thereof are also the same .

(In the general formula (X), R ³⁵ and R ³⁶ each independently represents a hydrogen atom or a monovalent substituent. R ³⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group. Represents an alkylsulfonyl group or an arylsulfonyl group, R ³⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and G ⁶ represents a steric parameter -Es ′ value of 1. Represents a monovalent substituent of 5 or more.)

In the general formula ^{(X), R 34, R} 35, R 36, R 37 and ^{G 6} is, ^R 34 in the general formula ^{(I), R 35, R} 36, and ^{R 37} and ^{G 6} have the same meanings, preferably The aspect is also the same.

Each of G ⁴ and G ⁶ has a steric parameter -Es' value of preferably 2.0 or more, more preferably 3.0 or more, still more preferably 4.0 or more, and particularly preferably 5 0.0 or more.
Specific examples of the substituent having a steric parameter -Es' value of 1.5 or more are given in Tables 1 to 3 of the present specification, but the present invention is not limited thereto.

(Specific examples of substituted pyrrole compounds)
Next, specific examples of the substituted pyrrole compound in the present invention are shown below, but the present invention is not limited thereto.

  Although the example of the synthesis | combining method of the pigment | dye compound represented by the said General formula (5) is shown below, this invention is not limited to these.

  The following exemplary compound M-7 was synthesized according to the following formulation according to the following synthesis scheme.

<Synthesis of Compound 1>
206.4 g of isobromomethyl ketone was stirred in 1 L of methanol, 7 mL of hydrobromic acid (47-49% aqueous solution) was added, and bromine was added dropwise over 3 hours at 30-34 ° C. Then, it stirred at 30 degreeC for 30 minutes. After neutralization with an aqueous solution in which 124 g of sodium hydrogen carbonate was dissolved in 1.3 L of water, an aqueous solution in which 400 g of sodium chloride was dissolved in 1.3 L of water was added, and the separated liquid reaction product was fractionated.
Separately, 222 g of potassium phthalimide was stirred in 800 mL of dimethylacetamide (DMAc), and the reaction product collected earlier was added dropwise under water cooling, followed by stirring at room temperature for 4 hours. Thereafter, 720 mL of water was added under water cooling, and the precipitated crystals were separated by filtration. The obtained crystals were suspended in 1.5 L of toluene, insoluble matters were filtered off, and the filtrate was concentrated to obtain Compound 1 (100 g).
Compound 1: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.21-1.23 (6H, d), 2.74-2.79 (1H, m), 4.56 (2H, s ), 7.72-7.74 (2H, d), 7.85-7.87 (2H, d).

<Synthesis of Compound 2>
The compound was synthesized by the method described in paragraph 0134 of JP-A-2008-292970.

<Synthesis of Compound 3>
Compound 2 (293 g) and Compound 1 (231 g) were stirred in 1.4 L of methanol under a nitrogen atmosphere, and sodium hydroxide (88 g) was dissolved in 400 ml of water and added dropwise at room temperature. Thereafter, the mixture was refluxed for 8 hours. Thereafter, the mixture was allowed to cool to room temperature, and the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain Compound 9 (299 g).
Compound 3: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.88 to 0.95 (18H, s), 1.00 to 1.03 (3H, d), 1.17 to 1.19 (6H, d), 1.20 to 1.66 (7H, m), 3.38 to 3.43 (1H, m), 5.19 to 5.24 (2H, br), 5.95 (1H Br), 6.00 (1H, s), 7.39-7.45 (1H, br).

<Synthesis of Compound 4>
N, N-diisopropylamine (11.1 g) in dehydrated tetrahydrofuran 80 mL,
The mixture was stirred under a nitrogen atmosphere, and a 1.6 mol / L butyllithium hexane solution (66 mL) was added dropwise at −40 ° C. over 10 minutes. After stirring for 1 hour, ethyl 2-ethylbutyric acid (14.4 g) was added dropwise at −20 ° C. over 15 minutes, and the temperature was raised to 0 ° C. After stirring for 1 hour, ethyl iodide (17.2 g) was added dropwise over 10 minutes. After completion of the reaction, 40 mL of 1M aqueous hydrochloric acid solution was added, extracted with 100 mL of ethyl acetate, and washed with 80 mL of water and 80 mL of saturated brine. The organic layer was dehydrated with 15 g of magnesium sulfate and filtered, and then the filtrate was concentrated to dryness to obtain Compound 4 (17.9 g).
Compound 4: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.76 (9H, t), 1.25 (3H, t), 1.57 (6H, q), 4.13 (2H, q)

<Synthesis of Compound 5>
Compound 4 (17.6 g) and potassium hydroxide (16.8 g) were dissolved in water (5 mL) and ethanol (30 mL), and the mixture was stirred with heating under reflux for 8 hours. Thereafter, 20 mL of water was added, and concentrated hydrochloric acid was added until the pH of the aqueous layer was about 1. After extraction with 100 mL of ethyl acetate, it was washed with 80 mL each of water and saturated brine. The organic layer was dehydrated with 20 g of sodium sulfate, filtered, and the filtrate was concentrated to dryness to obtain Compound 5 (13.0 g).
Compound 5: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.81 (9H, t), 1.60 (6H, q)

<Synthesis of Compound 6>
Compound 5 (2.6 g) was stirred in 3 mL of methylene chloride, and thionyl chloride (2.6 g) was added dropwise at room temperature over 10 minutes. After 1 hour, the reaction solution was distilled at 8000 Pa and 40 ° C. to obtain Compound 6 (1.8 g).
Compound 6: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.85 (9H, t), 1.70 (6H, q)

<Synthesis of Compound N-1 (Compound 7 in the above scheme)>
Compound 3 (2.1 g) was stirred in 6 mL of dimethylacetamide (DMAc) at room temperature, 0.99 g of compound 6 was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into 10 mL of ethyl acetate and 20 mL of water, washed with 15 mL each of saturated aqueous sodium bicarbonate, water, and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrate was purified by column chromatography and concentrated under reduced pressure to obtain Compound 7 (2.2 g).
Compound N-1: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.82 (9H, t), 0.90 (18H, s), 1.02 (3H, d), 1.20— 1.70 (19H, m), 3.47 (1H, quint), 6.02 (1H, s), 6.21 (1H, s), 10.59 (1H, s), 10.88 (1H) , S)

<Synthesis of Compound O-1 (Compound 8 in the above scheme)>
While stirring N-methylformanilide (0.28 g) and acetonitrile (1.0 mL) at 0 ° C. while keeping phosphorus oxychloride (0.32 g) at 5 ° C. or lower, and stirring for 1 hour, compound 7 (0 .50 g) and 1.0 mL of acetonitrile were added and stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The reaction solution was poured into 15 mL of water, and the precipitated crystals were filtered and washed with 10 mL of water to obtain Compound 8 (0.40 g).
Compound O-1: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.84 (9H, t), 0.89 (18H, s), 1.03 (3H, d), 1.20— 1.70 (7H, m), 1.43 (6H, d), 1.68 (6H, q), 4.13 (1H, quint), 6.04 (1H, s), 9.87 (1H , S), 10.95 (1H, s), 11.19 (1H, s)

<Synthesis of Compound M-148>
Compound N-1 (0.27 g), compound O-1 (0.28 g) and 5 ml of acetic anhydride were stirred at room temperature, and 0.90 g of trifluoroacetic acid was added dropwise. After stirring at room temperature for 4 hours, 30 mL of water and 5 g of sodium hydrogen carbonate were stirred at room temperature, and the reaction solution was gradually poured into the solution for neutralization. After stirring for 1 hour, the precipitated crystals were filtered and washed with 10 mL of water to obtain Compound M-148 (0.44 g). The absorption maximum wavelength in the absorption spectrum of M-148 in ethyl acetate was 519 nm, and the molar extinction coefficient was 46000.
Compound M-148: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.86 (18H, t), 0.87 (36H, s), 1.02 (6H, d), 1.20— 1.73 (14H, m), 1.40 (12H, d), 1.69 (12H, q), 4.17 (2H, quint), 6.01 (2H, s), 7.50 (1H) , S), 10.51 (2H, s)

<Synthesis of Exemplified Compound M-7>
Compound M-148 (0.42 g) and 15 mL of tetrahydrofuran were stirred at room temperature, and a solution of zinc lactate trihydrate (0.122 g) dissolved in 5 mL of methanol was added dropwise thereto and stirred for 2.5 hours. Thereafter, the solvent is distilled off from the reaction solution by reducing the pressure at 35 ° C. and 0.013 MPa for 10 minutes with an evaporator, 10 ml of water is added to the remaining solution, the precipitated crystals are filtered and dried, and exemplified compound M-7 ( 0.21 g) was obtained. The absorption maximum wavelength in the absorption spectrum of M-7 in ethyl acetate was 545 nm, and the molar extinction coefficient was 156000.
Exemplary Compound M-7: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.83 (18H, t), 0.89 (36H, s), 1.02 (6H, d), 1.18 -1.80 (41H, m), 4.01 (1H, q), 4.24 (2H, quint), 6.03 (2H, s), 7.76 (1H, s), 11.27 ( 2H, s)

  The following exemplary compound M-53 was synthesized according to the following formulation according to the following synthesis scheme.

<Synthesis of Compound 9>
N, N-diisopropylamine (30 g) was stirred in 200 mL of dehydrated tetrahydrofuran under a nitrogen atmosphere, and a 1.6 mol / L butyllithium hexane solution (186 mL) was added dropwise at −60 ° C. over 20 minutes. After stirring at −40 ° C. for 30 minutes, ethyl 2-ethylbutyrate (39 g) was added dropwise over 10 minutes. After stirring for 30 minutes, the mixture was cooled to −78 ° C., 1-bromo-3-chloropropane (47 g) was added dropwise over 15 minutes, and the temperature was slowly raised to room temperature over 4 hours. 1 M hydrochloric acid aqueous solution was added after completion | finish of reaction, it extracted with ethyl acetate 400 ml, and it wash | cleaned with 200 mL of 1M hydrochloric acid aqueous solution, 200 mL of water, and 200 mL of saturated salt solution. The organic layer was dehydrated with 15 g of magnesium sulfate, filtered, and the filtrate was concentrated. The concentrate was purified by column chromatography and concentrated under reduced pressure to give compound 9 (45 g).
Compound 9: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.79 (6H, t), 1.25 (3H, t), 1.57 (4H, q), 1.40-1. 65 (4H, m)
3.52 (2H, t) 4.15 (2H, q),

<Synthesis of Compound 10>
Compound 9 (17.2 g) was added dropwise in 80 mL of acetonitrile at room temperature over 10 minutes, followed by stirring at 80 ° C. for 60 hours. Thereafter, the reaction solution was added dropwise to 400 mL of water over 30 minutes. The mixture was extracted with 500 ml of ethyl acetate, washed with 300 mL each of saturated aqueous sodium hydrogen carbonate, water, and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrate was purified by column chromatography and concentrated under reduced pressure to give compound 10 (8.6 g).
Compound 10: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.80 (6H, t), 1.57-1.82 (8H, m), 3.52 (2H, t)

<Synthesis of Compound 11>
Compound 10 (5.8 g) was dissolved in 10 mL of dichloromethane, and thionyl chloride (7.1 g) was added dropwise over 10 minutes in an ice bath and nitrogen atmosphere. After reacting at room temperature for 2 hours, the reaction solution was distilled (11 mmHg, 80 ° C.) to obtain Compound 11 (5.7 g).
Compound 11: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.87 (6H, t), 1.62-1.83 (8H, m), 3.55 (2H, t)

<Synthesis of Compound N-77 (Compound 12 in the above scheme)>
Compound 3 (194 g) was dissolved in 1900 ml of acetonitrile under a nitrogen atmosphere, and then triethylamine (63 g) was added while stirring at room temperature, and further compound 11 (120 g) was added dropwise over 10 minutes. Then, it heated at 80 degreeC and stirred for 6 hours. After cooling to room temperature, 950 mL of water was poured into the reaction solution, and the precipitated solid was filtered. Next, 950 mL of methanol was poured into the obtained solid, and suspension washing was performed by heating to 70 ° C. and stirring. After cooling to room temperature, compound N-77 (260 g) was obtained by filtration.
Compound N-77: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.86 (6H, t), 0.90 (18H, s), 1.02 (3H, d), 1.21 ( 6H, d), 1.25-1.73 (15H, m), 3.45 (1H, quint), 6.02 (1H, s), 6.20 (1H, s), 10.52 (1H , S), 10.94 (1H, s)

<Synthesis of Compound N-52 (Compound 13 in the above scheme)>
Compound 12 (18.0 g) and thiomalic acid (7.9 g) were added to 70 mL of dimethylacetamide, stirred at room temperature, and added dropwise over 30 minutes while maintaining diazabicycloundecene (26.8 g) at 30 ° C. or lower. . After stirring at room temperature for 12 hours, 0.5N HClaq in an ice bath
The reaction solution was added dropwise to 400 mL over 30 minutes. The precipitated solid was filtered, washed with water, stirred again in 400 mL of water, and filtered. The obtained solid was vacuum-dried (45 ° C., 12 hours) to obtain Compound N-52 (18.4 g).
Compound N-52: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.86 (6H, t), 0.89 (18H, s), 1.02 (3H, d), 1.18- 1.80 (21H, m), 2.61-2.80 (3H, m), 2.98 (1H, td), 3.46 (1H, quint), 3.64 (1H, dd), 6 .01 (1H, s), 6.23 (1H, s), 10.61 (1H, s), 10.94 (1H, s)

<Synthesis of Compound N-61 (Compound 14 in the above scheme)>
Compound 12 (22.0 g), methacrylic acid (6.9 g), potassium iodide (6.6 g) and paramethoxyphenol (11.5 mg) were added to 50 mL of dimethylacetamide and stirred at room temperature. After adding triethylamine (10.1 g), the internal temperature was heated to 85 ° C., and the mixture was stirred at that temperature for 4 hours. After completion of the reaction, 75 mL of ethyl acetate was added and 1N HC
After washing with 50 mL each of laq, water and saturated aqueous sodium hydrogen carbonate, the mixture was concentrated under reduced pressure. The obtained solid was recrystallized with 100 mL of acetonitrile to obtain Compound N-61 (16.5 g).
Compound N-61: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.86 (6H, t), 0.89 (18H, s), 1.02 (3H, d), 1.27 ( 6H, d), 1.36 (4H, q), 1.73-1.93 (11H, m), 1.94 (3H, s), 3.46 (1H, quint), 4.14 (2H) , T), 5.54 (1H, s), 6.02 (1H, s), 6.09 (1H, s), 6.22 (1H, s), 10.54 (1H, s), 10 .94 (1H, s)

<Synthesis of Compound O-61 (Compound 15 in the above scheme)>
While stirring N-methylformanilide (4.3 g) in 25 mL of acetonitrile at 5 ° C., phosphorus oxychloride (4.9 g) was added dropwise, and after stirring for 1 hour, compound 14 (16.0 g) and 10 mL of acetonitrile were added. The mixture was stirred at room temperature for 30 minutes and then stirred at 40 ° C. for 5 hours. The reaction solution was poured into 300 mL of water and stirred for 1 hour. The precipitated solid was taken out and recrystallized from acetone to obtain Compound O-61 (10.3 g).
Compound O-61: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.86 (6H, t), 0.89 (18H, s), 1.03 (3H, d), 1.26 ( 4H, q), 1.42 (6H, d), 1.57-1.94 (11H, m), 1.93 (3H, s), 4.11 (1H, quint), 4.14 (2H , T), 5.55 (1H, s), 6.04 (1H, s), 6.10 (1H, s), 9.87 (1H, s), 11.01 (1H, s), 11 .16 (1H, s)

<Synthesis of Compound M-151>
Compound 13 (10.7 g), compound 15 (10.1 g) and 100 ml of acetic anhydride were stirred at room temperature, and 8.6 g of trifluoroacetic acid was added dropwise. After stirring at room temperature for 4 hours, 700 mL of water and 170 g of sodium hydrogen carbonate were stirred at room temperature, and the reaction solution was gradually poured into the solution for neutralization. After stirring for 1 hour, the precipitated crystals were filtered and washed with 300 mL of water. The obtained solid was dissolved again in 50 mL of tetrahydrofuran, 50 mL of water and triethylamine (10.5 g) were added to make a homogeneous system, and the mixture was stirred at room temperature for 10 minutes. To the reaction solution, 400 mL of ethyl acetate was added, washed twice with 1N HClaq × 2, 400 mL of water, and concentrated under reduced pressure. The obtained solid was blown and dried at 40 ° C. for 12 hours to obtain Compound M-151 (19.5 g). The absorption maximum wavelength in the absorption spectrum of M-151 in ethyl acetate was 519 nm, and the molar extinction coefficient was 44000.
Compound M-151: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.79-0.94 (48H, m), 1.02 (6H, d), 1.21-1.77 (22H , M), 1.42 (12H, d), 1.93 (3H, s), 2.59-2.78 (3H, m), 2.95 (1H, dd), 3.66 (1H, dd), 4.02-4.15 (4H, m), 5.54 (1H, s), 6.03 (2H, s), 6.11 (1H, s), 7.58 (1H, s) ), 10.75 (1H, s), 10.78 (1H, s)

<Synthesis of Exemplified Compound M-53>
Compound M-151 (19.0 g) was dissolved in 90 ml of THF under stirring at room temperature, and then 90 mL of methanol was added. A solution obtained by dissolving zinc acetate dihydrate (3.3 g) in 90 mL of methanol was added dropwise thereto over 10 minutes, and the mixture was stirred for 1 hour. Then, 90 mL of the solvent was distilled off from the reaction solution by reducing the pressure with an evaporator at 30 ° C. and 1000 Torr for 10 minutes. The remaining solution was added dropwise to 500 ml of water, and the precipitated crystals were filtered and dried to obtain Exemplified Compound M-53 (19.0 g). The absorption maximum wavelength in the absorption spectrum of M-53 in ethyl acetate was 545 nm, and the molar extinction coefficient was 150,000.
Exemplary Compound M-53: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.81-0.99 (48H, m), 1.02 (6H, d), 1.15-1.90 ( 34H, m), 1.94 (3H, s), 2.58-2.80 (3H, m), 3.00 (1H, d), 3.46 (1H, br), 4.14-4 .30 (4H, m), 5.53 (1H, s), 6.04 (1H, s), 6.06 (1H, s), 6.11 (1H, s), 7.80 (1H, s), 11.29 (1H, s), 11.45 (1H, s)

<Synthesis of Exemplified Compound I-12>
The following exemplary compound I-12 was synthesized according to the following formulation according to the following synthesis scheme.

2- (2 ′, 5′-dimethoxy-4′-nitrophenylazo) -4-isopropoxy-1-naphthol (19) synthesized by the method described in Example 3 of US Pat. No. 4,073,781. .2g) was dissolved in dimethylacetamide. While stirring at room temperature, 9.0 g of Compound 6 was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into 100 mL of ethyl acetate and 200 mL of water, washed with 150 mL of saturated aqueous sodium bicarbonate, water, and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrate was purified by column chromatography and concentrated under reduced pressure to give Exemplified Compound I-12 (22.9 g). The absorption maximum wavelength in the absorption spectrum of I-12 in ethyl acetate was 420 nm, and the molar extinction coefficient was 45000.
Compound I-12: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.90 (9H, t), 1.52 (6H, q), 3.73 (6H, s), 3.86 ( 3H, s), 7.35-8.25 (7H, m)

<Synthesis of Exemplified Compound J-10>
The following exemplary compound J-10 was synthesized according to the following formulation.
It was synthesized in the same manner as described in Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry, 1987, p. 815-818. The absorption maximum wavelength in the absorption spectrum of J-10 in ethyl acetate was 795 nm, and the molar extinction coefficient was 39000.
Compound J-10: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.85 (9H, t), 1.15 (6H, t), 1.63 (6H, q), 3.45 ( 4H, q), 6.80-7.38 (7H, m)

  Exemplary compounds M-20, M-22, M-35, M-93, M-45, M-46, M-78, M-146, N-4, N-15, N-17, N- The compound data of 30, N-36, N-37, N-69, O-30, O-37, and O-55 are shown. These dipyrromethene metal complexes and substituted pyrrole compounds utilize reactions similar to those shown in the above-mentioned synthesis of M-7, M-53 and their intermediates, see the synthesis method in the above scheme. And can be obtained by the same operation.

Exemplary compound M-20: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.89-0.97 (48H, m), 1.02 (6H, d), 1.18-1.80 ( 47H, m), 2.31 (2H, m), 2.95 (4H, t), 6.09 (2H, s), 7.17 (1H, s), 11.38 (2H, s)
The absorption maximum wavelength in the absorption spectrum in ethyl acetate was 542 nm, and the molar extinction coefficient was 130,000.

Exemplary Compound M-22: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.89-0.97 (54H, m), 1.02 (6H, d), 1.18-1.80 ( 39H, m), 2.05 (2H, quint), 2.31 (2H, m), 2.80 (4H, d), 6.10 (2H, s), 7.18 (1H, s), 11.43 (2H, s)
The absorption maximum wavelength in the absorption spectrum in ethyl acetate was 543 nm, and the molar extinction coefficient was 130,000.

Exemplary Compound M-35: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.89 (36H, s), 1.02 (6H, d), 1.18-1.80 (29H, m) 4.24 (2H, quint), 6.03 (2H, s), 7.30-7.93 (19H, m), 11.35 (2H, s)
The absorption maximum wavelength in the absorption spectrum in ethyl acetate was 556 nm, and the molar extinction coefficient was 132000.

Exemplary Compound M-45: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.88-4.41 (94H, m), 5.54 (1H, s), 5.83 (1H, s) , 6.03 (2H, s), 6.11 (1H, s), 6.39 (1H, s), 7.80 (1H, s), 11.40 (1H, s), 11.55 ( 1H, s)
The absorption maximum wavelength in the absorption spectrum in ethyl acetate was 546 nm, and the molar extinction coefficient was 140000.

Exemplary Compound M-46: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.88-4.15 (80H, m), 6.02 (2H, s), 7.78 (1H, s) 11.33 (2H, s)
The absorption maximum wavelength in the absorption spectrum in ethyl acetate was 548 nm, and the molar extinction coefficient was 150,000.

Exemplary Compound M-78: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.81-0.99 (48H, m), 1.02 (6H, d), 1.15-1.90 ( 34H, m), 2.58-2.80 (3H, m), 3.00 (1H, d), 3.46 (1H, br), 3.53 (2H, t), 4.20-4 .30 (2H, m), 6.04 (1H, s), 6.06 (1H, s), 7.80 (1H, s), 11.29 (1H, s), 11.45 (1H, s)

Exemplary Compound M-93: ¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.88-4.41 (86H, m), 5.72-5.8 (2H, br), 5. 82 (1H, s), 6.04 (1H, s), 6.88 (1H, s), 7.28-7.58 (10H, m), 10.41-10.49 (2H, br) .

Exemplary Compound M-146: ¹ H-NMR, 300 MHz, δ (CDCl ₃ ) ppm: 0.79-1.02 (54H, m), 1.15-1.90 (38H, m), 1.94 ( 6H, s), 2.75-4.13 (10H, m), 5.58 (1H, s), 6.04 (1H, s), 6.10 (1H, s), 6.18 (1H , S), 7.76 (1H, s), 11.38 (2H, s)
In the absorption spectrum in ethyl acetate, the absorption maximum wavelength was 545 nm, and the molar extinction coefficient was 130,000.

Compound N-4: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.82 (9H, t), 0.90 (18H, s), 0.98 (6H, d), 1.02 ( 3H, d), 1.20-1.70 (13H, m), 1.98 (1H, quint), 2.58 (2H, d), 6.02 (1H, s), 6.22 (1H , S), 10.43 (1H, s), 10.85 (1H, s)

Compound N-15: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.90-0.98 (24H, m), 1.02 (3H, d), 1.20-1.70 (22H M), 2.30 (1H, m), 2.71 (2H, d), 6.02 (1H, s), 6.21 (1H, s), 10.48 (1H, s), 10 .89 (1H, s)

Compound N-17: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.90-0.98 (27H, m), 1.02 (3H, d), 1.20-1.70 (18H M), 1.99 (1H, quint), 2.30 (1H, m), 2.56 (2H, d), 6.02 (1H, s), 6.21 (1H, s), 10 .53 (1H, s), 10.95 (1H, s)

Compound N-30: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.90 (18H, s), 1.02 (3H, d), 1.20-1.70 (13H, m), 3.48 (1H, quint), 6.03 (1H, s), 6.21 (1H, s), 7.30-7.93 (9H, m), 10.73 (1H, s), 10 .92 (1H, s)

Compound N-36: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.83 (9H, t), 0.90 (18H, s), 1.21 (6H, d), 1.20— 1.90 (13H, m), 2.80 (1H, dd), 3.02 (1H, dd), 3.39 (1H, quint), 3.48 (1H, d), 3.67 (1H) D), 3.90 (1H, dd), 4.08 (1H, d), 6.05 (1H, s), 6.22 (1H, s), 10.60 (1H, s), 10 .95 (1H, s)

Compound N-37: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.82 (9H, t), 0.90 (18H, s), 1.22 (6H, d), 1.20— 1.93 (13H, m), 1.95 (3H, s), 3.40 (1H, quint), 4.03 (2H, d), 5.59 (1H, s), 6.10 (1H , S), 6.18 (1H, s), 6.21 (1H, s), 10.58 (1H, s), 10.95 (1H, s)

Compound N-69: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.77-1.68 (38H, m), 1.91 (3H, s), 2.92 (2H, t), 4.56 (2H, t), 5.52 (1H, s), 5.89 (1H, s), 6.08 (1H, s), 6.33 (1H, s), 7.27-7 .38 (5H, m), 10.80 (1H, br), 11.40 (1H, br).

Compound O-30: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.89 (18H, s), 1.03 (3H, d), 1.20-1.70 (13H, m), 4.14 (1H, quint), 6.04 (1H, s), 7.29-7.94 (9H, m), 9.87 (1H, s), 11.05 (1H, s), 11 .29 (1H, s)

Compound O-37: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.83 (9H, t), 0.90 (18H, s), 1.21 (6H, d), 1.20— 1.93 (13H, m), 1.95 (3H, s), 3.98-4.15 (3H, m), 5.59 (1H, s), 6.10 (1H, s), 6 .18 (1H, s), 9.89 (1H, s), 10.95 (1H, s), 11.20 (1H, s)

Compound O-55: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.75-1.69 (38H, m), 2.55-3.80 (3H, t), 5.91 (1H , S), 7.28-7.37 (5H, m), 9.06 (1H, s), 10.94 (1H, br), 11.15 (1H, br).

Examples of the method for synthesizing the dye multimer represented by the general formula (1) are shown below, but the present invention is not limited thereto.
<Synthesis of Exemplified Compound P51>
While stirring 5.21 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) at 80 ° C., exemplary compound M-53 (7.0 g), methacrylic acid (0.45 g), dodecanethiol (0.17 g) A solution of dimethyl 2,2′-azobis (2-methylpropionate) (0.096 g) in 12.2 g of PGMEA was added dropwise over 4 hours. Two hours after the completion of dropping, a solution in which dimethyl 2,2′-azobis (2-methylpropionate) (0.029 g) and dodecanethiol (0.051 g) were dissolved in 0.35 g of PGMEA was added, and 80 Stirring was continued for an additional 2 hours at ° C. To the reaction solution, 175 ml of PGMEA and 200 ml of methanol were added, and the reaction solution was added dropwise while stirring 800 ml of acetonitrile. The precipitated crystals were filtered, and the obtained crystals were dried under reduced pressure to obtain 3.99 g of exemplary compound P51. The obtained exemplary compound P51 had a weight average molecular weight (Mw) of 7000 and an acid value of 185 mgKOH / g.
The structure of Exemplified Compound P51 is confirmed by disappearance of peaks at 5.53 and 6.11, which are polymerizable group sites of M-53, and introduction of methacrylic acid by acid value measurement by ¹ H-NMR. did.

<Synthesis of Exemplified Compound P54>
Exemplified Compound M-53 (1.67 g), methacrylic acid (0.21 g) and dodecanethiol (0.076 g) were dissolved in 10.7 g of PGMEA and stirred at 85 ° C. while Exemplified Compound M-53 (3. 33 g), methacrylic acid (0.43 g), dodecanethiol (0.15 g), dimethyl-2,2′-azobis (2-methylpropionate) (0.52 g) dissolved in 21.3 g of PGMEA Was added dropwise over 3 hours. Four hours after the start of dropping, dimethyl-2,2′-azobis (2-methylpropionate) (0.047 g) was added, and stirring was continued at 85 ° C. for another 2 hours. To the reaction solution, 115 ml of PGMEA and 153 ml of methanol were added, and the reaction solution was added dropwise while stirring 614 ml of acetonitrile. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 1.75 g of exemplary compound P54. The obtained exemplary compound P54 had a weight average molecular weight (Mw) of 8000 and an acid value of 112 mgKOH / g.
The structure of Exemplified Compound P54 is confirmed by disappearance of the peaks of 5.53 and 6.11, which are polymerizable group sites of M-53, and introduction of methacrylic acid by acid value measurement by ¹ H-NMR. did.

<Synthesis of Exemplified Compound P101>
A solution of Exemplified Compound P51 (5.0 g), glycidyl methacrylate (0.47 g) and p-methoxyphenol (5.5 mg) dissolved in 31.0 g of PGMEA was heated and stirred at 100 ° C. for 5 hours. Next, the reaction solution was dropped into 350 ml of acetonitrile which was being stirred. The precipitated crystals were filtered, and the obtained crystals were dried under reduced pressure to obtain 3.59 g of Exemplified Compound P91. The obtained exemplary compound P91 had a weight average molecular weight (Mw) of 8000 and an acid value of 110 mgKOH / g.
The structure of Example Compound P101 was confirmed by ¹ H-NMR by disappearance of the epoxy moiety of glycidyl methacrylate and reduction of the acid value of the glycidyl methacrylate by acid value measurement. The dye compound having a polymerizable group may contain a dye compound before introducing the polymerizable group.

  Examples of the method for synthesizing the dye multimer represented by the general formula (B) are shown below, but the present invention is not limited thereto.

<Synthesis of Exemplified Compound S-50>
While stirring 5.21 g of PGMEA at 80 ° C., exemplary compound M-78 (7.0 g), methacrylic acid (0.90 g), dodecanethiol (0.34 g), dimethyl 2,2′-azobis (2-methylpro) A solution prepared by dissolving Pionate (0.192 g) in 12.2 g of PGMEA was added dropwise over 4 hours. Two hours after the completion of the dropwise addition, a solution of dimethyl 2,2′-azobis (2-methylpropionate) (0.058 g) and dodecanethiol (0.102 g) dissolved in 0.35 g of PGMEA was added, and 80 Stirring was continued for an additional 2 hours at ° C. To the reaction solution, 175 ml of PGMEA and 200 ml of methanol were added, and the reaction solution was added dropwise while stirring 800 ml of acetonitrile. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 5.0 g of Exemplified Compound S-50. The obtained exemplary compound S-50 had a weight average molecular weight (Mw) of 7,600 and an acid value of 190 mgKOH / g.
The structure of exemplary compound S-50 is that by ¹ H-NMR, the peak of 5.33 to 6.11 which is the polymerizable group site of M-78 is reduced, and methacrylic acid is introduced by acid value measurement. Confirmed by

  Examples of the method for synthesizing the dye multimer represented by the general formula (C) are shown below, but the present invention is not limited thereto.

<Synthesis of Exemplified Compound S-52>
Exemplified compound M-45 (11.5 g) and commercially available diisocyanate Q-1 (2.5 g) were mixed in N-methylpyrrolidone (100 ml) and stirred at 40 ° C. for 4 hours. To the reaction solution, 500 ml of methanol was added, and the reaction solution was added dropwise while stirring 800 ml of acetonitrile. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 7.6 g of Exemplary Compound S-52. The obtained exemplary compound S-52 had a weight average molecular weight (Mw) of 5,400.
Illustrative compound S-52 was confirmed by ¹ H-NMR by shifting the peak of the methylene at the α-position of the alcohol of M-45.

  Examples of the method for synthesizing the dye multimer represented by the general formula (D) are shown below, but the present invention is not limited thereto.

<Synthesis of Exemplified Compound S-58>
Exemplified compound M-46 (11.7 g), commercially available tetramercapto compound Q-2 (1.1 g) and diazabicycloundecene (DBU, 7.5 g) were mixed in N-methylpyrrolidone (100 ml). , And stirred at 40 ° C. for 4 hours. To the reaction solution, 500 ml of methanol was added, and the reaction solution was added dropwise while stirring 800 ml of acetonitrile. The precipitated crystals were filtered, and the obtained crystals were dried under reduced pressure to obtain 4.2 g of exemplary compound S-58.
The structure of S-58 obtained was confirmed by ¹ H-NMR.
Exemplary Compound S-58: ¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.88 (192H, s), 1.08-1.9 (176H, m), 2.1 (36H, s), 2.
3-3.4 (36H, m), 3.17 (4H, bs), 3.4-3.65 (4H, m), 4.28 (8H, bs), 6.03 (4H, s) 7.26 (4H, s), 7.53 (4H, s), 10.59-10.63 (8H, br).

<Synthesis of Exemplified Compound P-101>
A solution of Exemplified Compound P-51 (5.0 g), glycidyl methacrylate (0.47 g), and p-methoxyphenol (5.5 mg) dissolved in 31.0 g of PGMEA was heated and stirred at 100 ° C. for 5 hours. Next, the reaction solution was dropped into 350 ml of acetonitrile which was being stirred. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 3.59 g of Exemplified Compound P101. The obtained exemplary compound P-101 had a weight average molecular weight (Mw) of 8000 and an acid value of 110 mgKOH / g.
The structure of Example Compound P-101 was confirmed by disappearance of the epoxy moiety of glycidyl methacrylate and reduction of the acid value of glycidyl methacrylate by acid value measurement by ¹ H-NMR.

<Evaluation of heat resistance of dye compound>
[Example 1-1]
The heat resistance of the dye compound obtained in the present invention was evaluated as follows. The evaluation results are shown in Table 9 below.

Exemplified compound M-7 (25.0 mg) as a dye compound was dissolved in 225 mg of tetrahydrofuran (hereinafter referred to as THF), placed on an aluminum cup, placed on a hot plate at 100 ° C. and heated for 2 minutes to volatilize THF. Then, it was placed on a hot plate at 260 ° C. and heated for 3 minutes. Thereafter, the solid matter remaining in 200 mL of ethyl acetate was dissolved, and the change in absorbance (residual color ratio) at the maximum absorption wavelength before and after heating at 260 ° C. with a spectrophotometer carry5 (manufactured by Varian), and the chromaticity meter MCPD The color difference (ΔE ^* ab value) before and after heating was measured at −1000 (manufactured by Otsuka Electronics Co., Ltd.) to evaluate heat resistance.
The higher the remaining color rate and the smaller the ΔE ^* ab value, the better the heat resistance. The remaining color rate of 70% or more is good, the remaining color rate of 80% or more is preferable, and the remaining color rate of 90% or more is more preferable. Also, a ΔE ^* ab value of 15 or less is good, a ΔE ^* ab value of 10 or less is preferable, and a ΔE ^* ab value of 5 or less is most preferable.

[Examples 1-2 to 1-11, Comparative Examples 1-1 to 1-8]
In Example 1-1, evaluation was performed in the same manner as in Example 1-1 except that the exemplified compound M-7 was changed to a pigment compound described in Table 9 below (however, with equal mass). The evaluation results are shown in Table 9 below. The structures of comparative dyes 1 to 3, 7, and 8 in Table 9 below are shown below.
In Table 9, the substituent means a substituent corresponding to G ² in the general formula (5).

  Comparative dyes 1 to 3 utilize the reaction similar to the reaction in the above-described synthesis of M-7 and their intermediates, and can be obtained by the same operation. The comparative dye 7 utilizes a reaction similar to the reaction in I-12 shown above, and can be obtained by the same operation. Comparative dye 8 was synthesized in the same manner as described in Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry, 1987, p. 815-818.

<Evaluation of alkali resistance of dye compound>
[Example 2-1]
The alkali resistance of the dye compound was evaluated as follows. The evaluation results are shown in Table 10 below.

Illustrative compound M-7 (50.0 mg), which is a dye compound, was dissolved in 1 mL of ethyl acetate, and 1 mL of 1M NaOH was added thereto, followed by stirring at 30 ° C. for 5 hours. Then, after extracting with ethyl acetate and preparing so that the whole quantity might be set to 100 mL, the solution was diluted to 5 times volume using ethyl acetate. Separately, Exemplified Compound M-7 (50 mg) was dissolved in ethyl acetate so that the total amount was 100 mL, and the solution was diluted to 5 times volume with ethyl acetate. The difference in absorbance at the maximum absorption wavelength (residual color ratio) of both using a spectrophotometer carry5 (manufactured by Varian), and the color difference before and after heating using a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics) ΔE ^* ab value) was measured to evaluate alkali resistance.
The larger the remaining color ratio and the smaller the ΔE ^* ab value, the better the alkali resistance. The remaining color rate of 70% or more is good, the remaining color rate of 80% or more is preferable, and the remaining color rate of 90% or more is more preferable. Also, a ΔE ^* ab value of 15 or less is good, a ΔE ^* ab value of 10 or less is preferable, and a ΔE ^* ab value of 5 or less is most preferable.

[Examples 2-2 to 2-11, Comparative examples 2-1 to 2-5]
In Example 2-1, evaluation was performed in the same manner as in Example 2-1, except that the exemplified compound M-7 was changed to a pigment described in Table 10 below (however, with equal mass). The evaluation results are shown in Table 10. Comparative dyes 1 to 3, 7 and 8 in Table 10 are as described above.
In Table 10, the substituent means a substituent corresponding to G ² in the general formula (5).

  As shown in the above Tables 9 to 10, all the examples using the coloring compound of the present invention showed excellent heat resistance and excellent alkali resistance.

  Furthermore, a colored curable composition was prepared using the dye compound obtained in the present invention, and a color filter was further produced. This will be specifically described below. Unless otherwise specified, “part” and “%” are based on mass.

<Evaluation of heat resistance as a colored curable composition>
[Example 3-1]
(1) Preparation of glass substrate with undercoat layer CT-2000L solution (manufactured by FUJIFILM Electromaterials Co., Ltd.) as a coating solution for the undercoat layer on a silicon wafer substrate so that the film thickness after drying is 2 μm. The film was applied using a spin coater and heated and dried at 220 ° C. for 1 hour to form a cured film (undercoat layer).

(2) Preparation of colored curable composition I. Pigment Blue 15: 6 dispersion was prepared as follows. I. Pigment Blue 15: 6 11.5 parts (average primary particle diameter 55 nm), pigment dispersant BYK-161 (manufactured by BYK) 3.5 parts, and PGMEA 85 parts mixed liquid bead mill (zirconia beads 0 (3 mm diameter) for 3 hours to mix and disperse to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion. With respect to the pigment dispersion, the average primary particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 25 nm.
Next, the following components were mixed to obtain a colored curable composition.

CyH (cyclohexanone) 1.133 parts Benzyl methacrylate / methacrylic acid copolymer (20% CyH solution) 1.009 parts (molar ratio = 70: 30, weight average molecular weight 30000)
Fluorine-based surfactant (DIC Corporation F475, 1% CyH solution) 0.125 parts Oxime-based photopolymerization initiator (compound having the following structure) 0.087 parts Dye compound (Exemplary Compound M-7) 0. 183 parts Pigment Blue 15: 6 dispersion 2.418 parts solid content concentration 17.70%, pigment concentration 11.80%)
・ Glycerol propoxylate (1% CyH solution) 0.048 parts ・ Dipentaerythritol hexaacrylate 0.225 parts

(3) Exposure and development of colored curable composition (image formation)
Using the spin coater, the colored curable composition obtained in (2) above is dried on the undercoat layer of the glass substrate with the undercoat layer obtained in (1) so that the film thickness after drying becomes 0.6 μm. It was applied and prebaked at 100 ° C. for 120 seconds.
Next, using an exposure apparatus UX3100-SR (manufactured by USHIO INC.), The coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 2 μm with an exposure amount of 200 mJ / cm ² . After the exposure, development was performed using a developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post-baking was performed at 200 ° C. for 15 minutes.

(4) Evaluation The heat resistance of the coating film coated on the glass substrate with the undercoat layer using the colored curable composition was evaluated as follows. The evaluation results are shown in Table 11 below.

〔Heat-resistant〕
The glass substrate coated with the colored curable composition obtained in the above (3) was placed on a hot plate at 200 ° C. so as to be in contact with the substrate surface and heated for 1 hour, and then a spectrophotometer carry5 (Varian) Change in absorbance at the maximum absorption wavelength before and after heating (residual color rate), and color difference before and after heating (ΔE ^* ab value) with the chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) Was evaluated as an index for evaluating heat resistance.
The larger the remaining color ratio and the smaller the ΔE ^* ab value, the better the alkali resistance. The remaining color rate of 70% or more is good, the remaining color rate of 80% or more is preferable, and the remaining color rate of 90% or more is more preferable. Also, a ΔE ^* ab value of 15 or less is good, a ΔE ^* ab value of 10 or less is preferable, and a ΔE ^* ab value of 5 or less is most preferable.
The ΔE ^* ab value is a value obtained from the following color difference formula based on the CIE 1976 (L ^* , a ^* , b ^* ) space color system (Japanese Society for Color Science, New Color Science Handbook (Showa 60)) p. 266).
ΔE ^* ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2

[Examples 3-2 to 3-20, Comparative examples 3-1 to 3-3]
In the preparation of the colored curable composition of Example 3-1 (2), Example 3-1 was used except that Exemplified Compound M-7 was changed to the colorant described in Tables 11 and 12 below (but with equal mass). A pattern was formed in the same manner as described above, and the same evaluation was performed. The evaluation results are shown in Table 11 and Table 12. Comparative dyes 1 to 3 in Table 11 are as described above.
In Table 11, the substituent means a substituent corresponding to G ² in the general formula (5).
The dye compound of Table 12 is a substituent further substituted with a substituent having an -Es 'value of 1.5 or more, and the -Es' value of the dye compound of Table 12 is 1.5 or more.

[Examples 3-21 to 3-25]
In the preparation of the colored curable composition of Example 3-1 (2), the pigment dispersant BYK-161 was changed to a dispersant described in Table 13 below (however, with equal mass), and the exemplified compound M-7 was further changed to A pattern was formed in the same manner as in Example 3-1, except that the colorant was changed to the colorant described in Table 13 below (however, with equal mass), and the same evaluation was performed. The evaluation results are shown in Table 13. Further, the dispersants 1 to 3 will be described in the section on the synthesis of the dispersants 1 to 3.

  From Tables 11, 12, and 13, it can be seen that the colored curable composition using the dye compound of the present invention can provide a color filter having good heat resistance.

<Synthesis of Dispersant 1>
Into a 500 mL three-necked flask, 600.0 g of ε-caprolactone was introduced and 22.8 g of 2-ethyl-1-hexanol was introduced and dissolved while stirring while blowing nitrogen. Monobutyltin oxide 0.1g was added and it heated at 100 degreeC. After 8 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by gas chromatography. 26. 2-methacryloyloxyethyl isocyanate after adding 0.1 g of 2,6-di-t-butyl-4-methylphenol
2g was added. After 5 hours, the disappearance of the raw material was confirmed by ¹ H-NMR, and then cooled to room temperature, to obtain 200 g of a solid precursor compound shown below. It is a precursor compound that ¹ H-N
Confirmed by MR, IR, and mass spectrometry.

Precursor compound 80.0 g, methacrylic acid 20.0 g, dodecyl mercaptan
3 g and 233.3 g of propylene glycol monomethyl ether acetate were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask at 75 ° C. The temperature was raised to. To this was added 0.2 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Two hours later, 0.2 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of Dispersant 1 was obtained.

  Dispersants 2 and 3 were synthesized in the same manner as Dispersant 1.

Claims (29)

A dye compound having a partial structure represented by the following general formula (5).

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents an integer of 1 to 8. When p is 2 or more, the structures in parentheses may be the same or different.R represents a hydrogen atom or a monovalent substituent.) The dye compound according to claim 1, wherein the partial structure represented by the general formula (5) is a partial structure represented by the following general formula (6).

(In General Formula (6), Dye represents a dye structure, G ¹ represents a nitrogen atom or an oxygen atom, G ³ represents a carbon atom, a sulfur atom, an oxygen atom, or a nitrogen atom. P represents 1 or 2) , When p is 2, the structures in parentheses may be the same or different.)   Dye in the general formula (5) is an azo dye, azomethine dye, dipyrromethene dye, quinone dye, carbonium dye, quinoneimine dye, azine dye, polymethine dye, quinophthalone dye, phthalocyanine dye, perinone dye, indigo dye, thioindigo dye, The dye compound according to claim 1 or 2, which is a residue of a dye compound selected from the group consisting of quinoline dyes, nitro dyes, nitroso dyes, and metal complex compounds thereof.   The Dye in the general formula (5) is a residue of a dipyrromethene compound, or a residue of a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. The dye compound described. The dye compound according to claim 4, wherein the dipyrromethene metal complex compound is a dipyrromethene metal complex compound represented by the following general formula (M) and a metal or metal compound, or a tautomer thereof.

(In the general formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent, and at least one substituent of R ^{4 to} R ¹⁰ is the same as G ¹ in the general formula (5). (However, R ⁴ and R ⁹ are not bonded to each other to form a ring.) The dipyrromethene metal complex compound obtained from the dipyrromethene compound of the general formula (M) and a metal or metal compound, and a tautomer thereof are represented by the following general formula (7) or general formula (8). The dye compound according to claim 4 or 5, which is a compound or a tautomer thereof.

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2. When a is 2, the structures of X ³ are the same or different. May be.) The dye compound according to claim 6, wherein R ¹¹ and R ¹⁶ in the general formula (8) are each independently a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more.   Furthermore, the pigment | dye compound of any one of Claims 1-7 which has a polymeric group.   Ma in said general formula (7) or general formula (8) is any one of Zn, Co, V = O, or Cu, The pigment | dye compound of any one of Claims 6-8 .   Ma in the said General formula (7) or General formula (8) is Zn, The pigment | dye compound of any one of Claims 6-9.   Furthermore, the pigment | dye compound of any one of Claims 1-10 which has an alkali-soluble group.   A dye compound which is a dye multimer comprising a group obtained by removing 1 to 10 hydrogen atoms from the dye compound according to any one of claims 1 to 11 as a partial structure of the dye part. Claims comprising at least one of the structural units represented by the following general formula (A), general formula (B) and general formula (C), or represented by the following general formula (D) 12. The dye compound according to 12.

(In General Formula (A), X ^A1 represents a linking group formed by polymerization, and L ^A1 represents a single bond or a divalent linking group. Dye II is derived from the partial structure represented by General Formula (5). A linking group having a structure in which 1 to (m1 + 1) hydrogen atoms are removed, and Dye in the general formula (5) is obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound It is a dye structure obtained by removing 1 to p arbitrary hydrogen atoms of a dipyrromethene metal complex compound, p represents 1 or 2, X ^A2 represents a linking group formed by polymerization, and L ^A2 represents a single bond or a divalent group. M1 represents an integer of 0 to 3. When m1 is 2 or more, [
The structure in] may be the same or different. DyeII the and L ^A2, covalent bonds are linked by either an ionic bond, and coordinate bond. )

(In the general formula (B), X ^B1 represents a linking group formed by polymerization, L ^B1 represents a single bond or a divalent linking group, and A represents a group capable of ionic bond or coordinate bond with DyeIII. DyeIII is a linking group having a structure obtained by removing 1 to (m2 + 1) hydrogen atoms from the partial structure represented by the general formula (5), and the Dye in the general formula (5) is represented by the following general formula (M ) Is a dye structure in which p hydrogen atoms have been removed from a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound, wherein p represents 1 or 2. X ^B2 is formed by polymerization. L ^B2 represents a single bond or a divalent linking group, and m2 represents an integer of 0 to 3. When m2 is 2 or more, the structures in [] are the same or different. also a good .DyeIII and ^{L B} And is a covalent bond, are connected in any of ionic bond, and coordinate bond.)

(In the general formula (C), L ^C1 represents a single bond or a divalent linking group. DyeIV is a linking group having a structure in which two hydrogen atoms are removed from the partial structure represented by the general formula (5). And Dye in the general formula (5) is a dye structure in which p hydrogen atoms of a dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the following general formula (M) and a metal or metal compound are removed. P represents 1 or 2. m3 represents an integer of 1 to 4. When m3 is 2 or more, L ^C1 may be the same or different.

(In General Formula (D), L ^D1 represents an m4-valent linking group, and m4 represents an integer of 2 to 100. When m4 is 2 or more, the structures of DyeV may be the same or different. DyeV is a linking group having a structure in which one hydrogen atom is removed from the partial structure represented by the general formula (5), and Dye in the general formula (5) is represented by the following general formula (M). (A dye structure in which p hydrogen atoms have been removed from a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. P represents 1 or 2.)

(In General Formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent, and a hydrogen atom is removed from at least one substituent of R ^{4 to} R ¹⁰ , provided that R ⁴ And R ⁹ are not bonded to each other to form a ring.) The dye compound according to claim 13, wherein the constituent unit represented by the general formula (A) is a constituent unit derived from a dye monomer represented by the following general formula (1).

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound and a metal or metal compound which is a linking group having a structure in which one hydrogen atom is removed from a partial structure, and Dye in the general formula (5) is represented by the following general formula (7) or (8) The dye structure is obtained by removing p arbitrary hydrogen atoms from the dipyrromethene metal complex compound obtained from the above. ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. metal atom, or a metal compound represented .R ^18, R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group .R ¹¹ of or an arylsulfonyl group, And R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. of X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2.   The dye compound according to claim 14, comprising a monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond as a copolymerization component.   Furthermore, the pigment | dye compound of any one of Claims 12-15 which has an alkali-soluble group.   A dye multimer comprising at least one of the structural units represented by the general formula (A), the general formula (B), and the general formula (C), and a large amount of the dye represented by the general formula (D). Body, a dye monomer represented by the general formula (1), and a monomer having a structure different from that of the dye monomer represented by the general formula (1) and having a terminal ethylenically unsaturated bond, The coloring matter compound according to claim 16, wherein at least one selected from the group consisting of has an alkali-soluble group.   DyeII in the general formula (A), DyeIII in the general formula (B), DyeIV in the general formula (C), DyeV in the general formula (D), or DyeVI in the general formula (1) is an alkali-soluble group. The dye compound according to claim 16 or 17, which has   In any one of Claims 12-18 containing the polymeric group introduce | transduced by adding the compound which has a group and a polymeric group which react with the substituent contained in the said pigment | dye compound to the said pigment | dye compound. The dye compound described. A dipyrromethene compound represented by the following general formula (I) is obtained by reacting a dipyrromethene compound represented by the following general formula (XI) with a metal derivative represented by the following general formula (XIII). A method for producing a metal complex compound.

(In General Formula (I), G ⁴ and G ⁶ each independently represent a monovalent substituent having a steric parameter of -Es ′ value of 1.5 or more. R ³² , R ³³ , R ³⁵ , and R ³⁶ each independently represent a hydrogen atom, or ^{.R 37} representing a monovalent substituent include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic represents a group ^{.R 31, R 34} are each independently hydrogen Represents an atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, Ma represents a metal atom or a metal compound, and X ³ represents a group capable of bonding to Ma. And a represents 0, 1, or 2.)

(In the general formula ^{(XI), R} 31 ~R ³⁷ and ^G 4, ^{G 6} are the same respectively ^R 31 ^{to R 37} and ^G 4, ^{G 6} in the general formula (I).)

(In the general formula (XIII), Ma and X ¹ are respectively synonymous with Ma and X ³ in the general formula (I). B represents an integer of 1 to 4.) 21. The dipyrromethene compound represented by the general formula (XI) is obtained by reacting a compound represented by the following general formula (V) with a compound represented by the following general formula (X). A method for producing a dipyrromethene metal complex compound.

(In the general formula ^(V), R ^31, R ^{32, R 33,} and ^{G 4} is ^R 31 in the general formula ^(I), R ^32, R 33, and ^{G 4} are each synonymous.)

(In the general formula ^{(X), R 34, R} 35, R 36, R 37, and ^{G 6} is, ^R 34 in the general formula ^{(I), R 35, R} 36, R 37, and a ^{G 6} respectively synonymous is there.) The method for producing a dipyrromethene metal complex compound according to claim 21, wherein a compound represented by the general formula (X) is obtained by reacting a compound represented by the following general formula (IX) with an acylating agent.

(In the general formula ^{(IX), R 34, R} 35, R 36, and ^{G 6} is ^{R 34, R 35, R 36} in the general formula (I), and a ^{G 6} respectively the same.) By reacting a compound represented by the following general formula (V), a compound represented by the following general formula (IX), and a compound represented by the following general formula (XII), the above general formula (XI) The manufacturing method of the dipyrromethene metal complex compound of Claim 22 which obtains the dipyrromethene compound represented by this.

(In the general formula ^{(V), R 31, R} 32, R 33, and ^{G 4, R} 31 in the general formula ^{(I), R 32, R} 33, and ^{G 4} as the same meaning.)

(In the general formula ^{(IX), R 34, R} 35, R 36, and ^{G 6} is, ^R 34 in the general formula ^{(I), R 35, R} 36, and ^{G 6} as the same meaning.)

(In the general formula ^{(XII), R 37} has the same meaning as ^{R 37} in the general formula (I) ^{.R 38}
Represents an alkyl group or an aryl group. ) The leaving group X ¹¹ in the following general formula (IV) compounds represented by, by chemically substituent conversion, to form a substituent G ⁴ in the compound represented by formula (V), wherein The method for producing a dipyrromethene metal complex compound according to any one of claims 21 to 23, wherein a compound represented by the general formula (V) is obtained.

(In the general formula ^(IV), R ^31, R ^{32, R 33} carbon atoms ^{.R 39} and ^{R 40} respectively and ^{R 31,} R ^{32, R 33} is as defined in formula (I) are each independently 2 The above alkyl group, alkenyl group, aryl group, and heterocyclic group are represented, X ¹¹ represents a monovalent leaving group, and n represents an integer of 0 to 10.) The compound represented by the following general formula (IV) is obtained by reacting a compound represented by the following general formula (II) with a compound represented by the following general formula (III). A method for producing a dipyrromethene metal complex compound.

(In the general formula ^(II), R ^31, R ^{32, R 33} are each synonymous with ^{R 31,} R ^{32, R 33} in the general formula (I).)

(In the general formula (III), R ³⁹ , R ⁴⁰ , X ¹¹ and n are R ³ in the general formula (IV).
⁹ , R ⁴⁰ , X ¹¹ and n are synonymous. X ¹² represents a monovalent leaving group. ) The manufacturing method of the dye multimer which synthesize | combines a dye multimer by radical polymerization using the dye monomer represented by following General formula (1).

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound having a structure in which two hydrogen atoms are removed from the partial structure, and wherein Dye in the general formula (5) is represented by the following general formula (7) or (8): A dye structure in which p hydrogen atoms have been removed from the dipyrromethene metal complex compound obtained from 1. p represents 1 or 2. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. metal atom, or a metal compound represented .R ^18, R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group .R ¹¹ of or an arylsulfonyl group, And R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered or 7-membered ring. of X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2.

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents an integer of 1 to 8. When p is 2 or more, the structures in parentheses may be the same or different.R represents a hydrogen atom or a monovalent substituent.) Homopolymerizing a dye monomer represented by the following general formula (1), or a dye monomer represented by the following general formula (1) and a dye monomer represented by the general formula (1) A multimer is obtained by copolymerization with a monomer having a different structure and having a terminal ethylenically unsaturated bond, and then a compound having a group capable of reacting with the multimer and a polymerizable group is added to the multimer. A method for producing a polymerizable group-containing dye multimer in which a polymerizable group is introduced.

(In the general formula (1), R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Q ¹ represents —N (R ² ) C (═O) —, —OC (═O). ^{-, - C (= O)} N (R 2) -, - C (= O) O-, a group represented by the following general formula (2), a group represented by the following general formula (3), or the following Represents a group represented by the general formula (4), Q ² represents a divalent linking group, n1 and n2 each independently represent 0 or 1. DyeVI is represented by the general formula (5) A dipyrromethene compound having a structure in which two hydrogen atoms are removed from the partial structure, and wherein Dye in the general formula (5) is represented by the following general formula (7) or (8): A dye structure in which p hydrogen atoms have been removed from the dipyrromethene metal complex compound obtained from 1. p represents 1 or 2. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

(In the general formulas (2) to (4), R ²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. A plurality of R ²³ are each independently a hydrogen atom or a monovalent substituent. K represents an integer of 0 to 4. When k is 2 or more, R ²³ may be the same or different, and * represents —C (R ²¹ ) ═CH in the general formula (1). represents the position at which the group bonds to ₂ group and **, in the general formula (1) (the case of n2 = 0) ^{Q 2} or DyeVI and indicates the position at which the bond.)

(In General Formula (7), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other. And may form a 5-membered, 6-membered, or 7-membered ring together with Ma, provided that R ⁴ and R ⁹ are not bonded to each other to form a ring.)

(In General Formula (8), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent, R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. ¹¹ and R ¹⁸ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ¹⁶ and R ¹⁹ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. X ³ represents a group capable of binding to Ma, and a represents 0, 1, or 2. When a is 2, the structures of X ³ are the same or different. May be.)

(In General Formula (5), Dye represents a dye structure, G ¹ represents NR or an oxygen atom, and G ² represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more. p represents an integer of 1 to 8. When p is 2 or more, the structures in parentheses may be the same or different.R represents a hydrogen atom or a monovalent substituent.) The substituted pyrrole compound represented by the following general formula (V).

(In the general formula (V), R ³² and R ³³ each independently represents a hydrogen atom or a monovalent substituent. R ³¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group. Represents an alkylsulfonyl group or an arylsulfonyl group, and G ⁴ represents a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more.) The substituted pyrrole compound represented by the following general formula (X).

(In the general formula (X), R ³⁵ and R ³⁶ each independently represents a hydrogen atom or a monovalent substituent. R ³⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group. Represents an alkylsulfonyl group or an arylsulfonyl group, R ³⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and G ⁶ represents a steric parameter -Es ′ value of 1. Represents a monovalent substituent of 5 or more.)