TW201728695A - Coloring composition, color filter, pattern forming method, solid-state imaging device, image display device and dye polymer - Google Patents

Abstract

Provided is a coloring composition capable of manufacturing a cured film in which occurrence of color unevenness and defects is suppressed, a color filter, a pattern forming method, a solid-state imaging device, an image display device and a dye polymer. The coloring composition contains a dye polymer and a curable compound, wherein the dye polymer contains two or more hetero atoms, and one or more of the hetero atoms include a dye structure in which an azo group or aromatic ring group is bonded to a cationic hetero ring that is a nitrogen atom.

Description

Coloring composition, color filter, pattern forming method, solid-state imaging element, image display device, and pigment multi-body

The present invention is directed to a colored composition. Further, the present invention relates to a color filter, a pattern forming method, a solid-state imaging device, an image display device, and a dye multimer using a coloring composition.

In recent years, demand for solid-state imaging devices such as charge coupled devices (CCD) image sensors has increased significantly due to the spread of digital cameras and mobile phones with cameras. Use color filters as a key component of displays or optical components.

For example, Patent Document 1 to Patent Document 5 discloses that a color filter or the like is produced by using a yellow dye having an azo group or an aromatic ring group bonded to a hetero atom containing two or more hetero atoms. One or more of the structures are a cationic heterocyclic ring of a nitrogen atom. Further, Patent Document 6 describes that a color filter is produced using a coloring composition containing a dye multimer. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-145493 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2011-144493 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2011-144269 (Patent Document 4) Japanese Laid-Open Patent Publication No. 2012-158439 (Patent Document 5)

[Problems to be Solved by the Invention] When a cured film or a pattern is formed using the colored composition as described in Patent Documents 1 to 6 described above, the colored composition may be applied to the support. After drying and drying the body, the cured film is produced by exposure or the like after a period of time. However, according to the study by the inventors of the present invention, when a cured film is produced by performing a hardening treatment after placing a film (unhardened film) for a long period of time, color unevenness or defects are likely to occur in the obtained cured film. The film (unhardened film) is a film in which a coloring composition of the yellow dye described in Patent Documents 1 to 5 is applied to a support or the like and dried. The more the film is placed, the easier it is to produce defects or color unevenness in the obtained cured film. On the other hand, since the yellow dyes described in Patent Documents 1 to 5 have high polarity, compatibility with other components (curable compounds, resins, solvents, and the like) in the colored composition tends to decrease with time. Therefore, it is presumed that the yellow dye is phase-separated from other components at the time of standing, or agglomeration of a yellow dye or the like is generated, so that defects or color unevenness are easily generated in the cured film. Further, Patent Document 6 does not describe a study on defects or color unevenness accompanying placement.

Accordingly, an object of the present invention is to provide a coloring composition, a color filter, a pattern forming method, a solid-state imaging device, an image display device, and a dye multimer which can produce a cured film which suppresses color unevenness or defects. [Means for solving the problem]

As a result of intensive studies, the inventors of the present invention have found that a polymer compound having a cationic heterocyclic ring having one or more hetero atoms containing two or more hetero atoms and having a nitrogen atom can be made into a polymer. The object is described, thus completing the present invention. The present invention provides the following. <1> A coloring composition comprising a dye multimer and a curable compound, and the dye multimer comprises a dye structure having a structure in which an azo group or an aromatic ring group is bonded to two One or more hetero atoms and one or more hetero atoms are a cationic heterocyclic ring of a nitrogen atom. <2> The colored composition according to <1>, wherein the cationic heterocyclic ring is represented by the following formula (I); wherein the formula (I) [Chemical Formula 1] Y ^a represents a sulfur atom or -NR ^Ya -, Y ^b represents a nitrogen atom or -CR ^Yb -, and R ^a , R ^b , R ^Ya and R ^Yb each independently represent a hydrogen atom, a substituent, and an atomic group constituting a dye structure. a bonding site or a bonding site with an atomic group constituting the dye multimer, and R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb may be bonded to each other to form a ring; Either or the ring as a whole has a monovalent positive charge. <3> The coloring composition according to <1> or <2>, wherein the pigment structure is represented by the formula (Ia); Ht represents a cationic heterocyclic ring containing two or more hetero atoms and one or more of the hetero atoms is a nitrogen atom, L represents -N=N-, or an extended aryl group, B represents a substituent, X represents an anion, Ht, B and At least one of X has a bonding site with an atomic group constituting the dye multimer. <4> The coloring composition according to <1> or <2>, wherein the dye multimer has a dye structure represented by the formula (I-1); In the formula (I-1), R ¹ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ and R ⁹ to R ^{1 2} each independently represent a hydrogen atom or a substituent. a group, Y ¹ represents a sulfur atom or -NR ^{Y 1} -, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ to R ² , R ⁷ to R ^{1 2} , R ^Y1 and At least one of X has a bonding site with an atomic group constituting the dye multimer. <5> The coloring composition according to <1> or <2>, wherein the dye multimer has a dye structure represented by the formula (I-2); In the formula (I-2), R ^{1 01} , R ^{11 0} and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^{1 02} to R ^{1 05} , R ^{1 06} to R ^{1 09} Each independently represents a hydrogen atom or a substituent, and R ^{11 0} and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or -NR ^{Y 2} -, and R ^{Y 2} represents a hydrogen atom, an alkyl group, an aryl group or a hetero atom. The ring group, X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^{Y 2} and X has a bonding site with an atomic group constituting the dye multimer. (6) The coloring composition according to any one of <1> to <5> wherein the dye multimer is a repeating unit represented by the following formula (A) and represented by the following formula (C) At least one of the repeating units, or represented by the following formula (D); [Chemical 5] In the formula (A), A ¹ represents a main chain of a repeating unit, L ¹ represents a single bond or a divalent linking group, and DyeI represents an azo group or an aromatic ring group bonded to a hetero atom containing two or more hetero atoms. a dye structure of a structure in which one or more cationic heterocycles of nitrogen atoms are formed; [Chemical 6] In the formula (C), L ³ represents a single bond or a divalent linking group, and DyeIII represents a cationic group having an azo group or an aromatic ring group bonded to one or more hetero atoms including two or more hetero atoms and a hetero atom. a pigment structure of a heterocyclic structure, m represents 0 or 1; [Chemical 7] In the formula (D), L ⁴ represents a (n+k)-valent linking group, n represents an integer of 2 to 20, k represents an integer of 0 to 20, and DyeIV represents an azo group or an aromatic ring-based bond to be contained. a dye structure having a structure in which two or more hetero atoms and one or more hetero atoms are a cationic hetero ring of a nitrogen atom, and P represents a substituent. When n is 2 or more, a plurality of DyeIVs may be different from each other. When k is 2 or more, a plurality of Ps may be different from each other, and n+k represents an integer of 2 to 20. The colored composition according to any one of <1> to <6> wherein the dye multimer has a bis(sulfonyl) quinone imine anion or a tris(sulfonyl)methyl anion. The colored composition according to any one of <1> to <7> which further contains a pigment. The colored composition according to any one of <1> to <8> wherein the curable compound contains a radically polymerizable compound, and the colored composition further contains a photopolymerization initiator. The coloring composition according to any one of <1> to <9> which further contains an alkali-soluble resin. <11> A color filter using the coloring composition according to any one of <1> to <10>. <12> A pattern forming method comprising: a step of forming a colored composition layer on a support using the coloring composition according to any one of <1> to <10>; and a photolithography method Or a step of patterning the colored composition layer by dry etching. <13> A solid-state imaging element having the color filter according to <11>. <14> An image display device having the color filter according to <11>. <15> A dye multimer having a dye structure represented by the following formula (I-1) or formula (I-2); In the formula (I-1), R ¹ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ and R ⁹ to R ^{1 2} each independently represent a hydrogen atom or a substituent. a group, Y ¹ represents a sulfur atom or -NR ^{Y 1} -, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ to R ² , R ⁷ to R ^{1 2} , R ^Y1 and At least one of X has a bonding site with an atomic group constituting the dye multimer; [Chem. 9] In the formula (I-2), R ^{1 01} , R ^{11 0} and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^{1 02} to R ^{1 05} , R ^{1 06} to R ^{1 09} Each independently represents a hydrogen atom or a substituent, and R ^{11 0} and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or -NR ^{Y 2} -, and R ^{Y 2} represents a hydrogen atom, an alkyl group, an aryl group or a hetero atom. The ring group, X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^{Y 2} and X has a bonding site with an atomic group constituting the dye multimer. [Effects of the Invention]

According to the present invention, it is possible to provide a coloring composition, a color filter, a pattern forming method, a solid-state imaging device, an image display device, and a dye multimer capable of producing a cured film which suppresses color unevenness or defects.

Hereinafter, the contents of the present invention will be described in detail. In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "light" means actinic rays or radiation. In addition, the term "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron. Bunch and so on. In the present specification, the term "exposure" includes exposure to far ultraviolet rays, X-rays, EUV light, etc. represented by a mercury lamp or a quasi-molecular laser, and is performed by a particle beam such as an electron beam or an ion beam, unless otherwise specified. The depiction is also included in the exposure. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the colored composition. In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid. "(Meth)allyl" means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means two groups of an acryl group and a methacryl group. , or either. In the present specification, the term "step" is not only an independent step, but is also included in the term as long as the desired effect of the step is achieved even if it cannot be clearly distinguished from other steps. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present invention, the pigment means an insoluble compound which is difficult to dissolve in a specific solvent. Typically, it means a compound which exists in a state of being dispersed as a particle in a composition. Here, the solvent is, for example, a solvent exemplified in the solvent column described later.

<Coloring composition> The coloring composition of the present invention is a coloring composition containing a dye multimer and a curable compound, and the dye multimer includes a dye structure having a structure in which an azo group or an aromatic ring is used. The base bond is formed by a cationic heterocyclic ring containing two or more hetero atoms and one or more of the hetero atoms is a nitrogen atom. According to this configuration, even after the film (unhardened film) is left to be cured for a long period of time, it is possible to produce a cured film having few defects or color unevenness, and the film (unhardened film) is a coloring composition. A film applied to a support or the like and dried. Further, even if the uncured film is left for a long period of time and patterned, it is possible to obtain a pattern in which color unevenness, defects, and roughness of the pattern surface are small and pattern defects are suppressed. The reason for obtaining such an effect is presumed to be caused by the following. First, a dye compound having a structure in which an azo group or an aromatic ring group is bonded to a cationic hetero ring containing two or more hetero atoms and one or more hetero atoms are nitrogen atoms is often a highly polar dye. Compound. In particular, the five-membered ring structure having an asymmetry as a cationic heterocyclic dye compound has a very high polarity as compared with a highly symmetric xanthene, triarylmethane, cyanine or the like. On the other hand, the curable compound or the like used in the colored composition is often low in polarity. Therefore, it is considered that such a highly polar pigment compound is difficult to be compatible with other components in a coloring composition such as a curable compound. Further, since a dye compound having a dye structure in one molecule is likely to move in an uncured film, it is presumed that phase separation occurs during the placement due to the interaction of dipoles, or that the pigment compound is agglomerated and defects or colors are easily generated. equal. On the other hand, in the present invention, it is presumed that a dye compound having a structure in which an azo group or an aromatic ring group is bonded to the cationic hetero ring is polymerized to have a cationic impurity. A dye multimer of a dye structure of a ring, whereby the movement of the dye multimer in the film can be suppressed. Further, since the molecular weight is increased by the formation of the dye multimer, it is presumed that the polarity is smaller than that of the single molecule dye compound, and the compatibility with other components in the film is not easily lowered. Therefore, according to the present invention, even if the film is cured after being left for a long period of time (unhardened film), phase separation or aggregation at the time of standing can be suppressed, and as a result, a cured film in which color unevenness and defects are suppressed can be produced. The film (unhardened film) is a film in a state in which a coloring composition is applied to a support or the like and dried. Further, since phase separation or aggregation at the time of standing can be suppressed, the film can be uniformly cured after standing. Therefore, even if the uncured film is left for a long period of time and patterned, it is possible to obtain a pattern in which color unevenness, defects, and roughness of the pattern surface are small and pattern defects are suppressed. Hereinafter, the colored composition of the present invention will be described in detail.

<<Pigment Multimer>> The coloring composition of the present invention comprises a dye multimer having a dye structure having an azo group or an aromatic ring group bonded to a hetero atom containing two or more hetero atoms One or more of the structures are a cationic heterocyclic ring of a nitrogen atom. Further, in the present invention, the dye multimer includes a structure of a dimer, a trimer, a polymer, or the like. In addition, depending on the type of the dye structure (the type of the substituent which the cationic heterocyclic ring has, the type of the dye skeleton, etc.), the cation of the dye structure may be delocalized. The cationic heterocyclic ring in the present invention also contains a state in which a cation is delocalized.

The dye multimer of the present invention has two or more of the dye structures in one molecule, and preferably has three or more. The upper limit is not particularly limited, and may be set to 100 or less. The pigment structure in one molecule may be the same pigment structure or a different pigment structure. Further, in the present invention, the different dye structure includes not only a dye structure having a different dye skeleton but also a dye structure having the same pigment skeleton and different types of substituents bonded to the dye skeleton.

The cationic heterocyclic ring is preferably represented by the following formula (I). Formula (I) [10] Y ^a represents a sulfur atom or -NR ^Ya -, Y ^b represents a nitrogen atom or -CR ^Yb -, and R ^a , R ^b , R ^Ya and R ^Yb each independently represent a hydrogen atom, a substituent, and an atomic group constituting a dye structure. a bonding site or a bonding site with an atomic group constituting the dye multimer, and R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb may be bonded to each other to form a ring; Either or the ring as a whole has a monovalent positive charge.

The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. For example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc. are mentioned. The ring formed by bonding R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb may be a single ring or a polycyclic ring. The ring is preferably an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, and a thiazole ring. , imidazole ring, pyrazole ring, anthracene ring, indazole ring and the like. The aromatic ring is preferably a hydrocarbon aromatic ring, more preferably a benzene ring.

Specific examples of the cationic heterocyclic ring include the following (1) to (6). [11] R ^a1 to R ^a23 each independently represent a hydrogen atom, a substituent, a bonding site with an atomic group constituting the dye structure, or a bonding site with an atomic group constituting the dye multimer. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. For example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc. are mentioned.

Examples of the azo group bonded to the cationic heterocyclic ring include a group represented by -N=N-R. R represents a substituent. The substituents may be exemplified by the groups listed in the group of substituents A described later. For example, an aryl group, a heterocyclic group and an amine group are preferred.

Examples of the aromatic ring group bonded to the cationic heterocyclic ring include a hydrocarbon aromatic ring group and a heteroaromatic ring group. Examples of the hydrocarbon aromatic ring group include a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthrene ring group. Examples of the heteroaromatic ring group include a pyridine ring group, a pyrazine ring group, a pyrrole ring group, a quinoline ring group, a quinoxaline ring group, a furan ring group, a benzofuran ring group, a thiophene ring group, and a benzo group. A thiophene ring group, an oxazole ring group, a thiazole ring group, an imidazole ring group, a pyrazole ring group, an anthracenyl group, an indazole ring group and the like. The aromatic ring group is preferably a hydrocarbon aromatic ring group, more preferably a benzene ring group. The aromatic ring group may have a substituent or may be unsubstituted. The substituents may be exemplified by the groups listed in the group of substituents A described later. It is preferably an electron donating group. Examples of the electron-donating group include a group having a σp value of 0.2 or less by Hammett. The σp value is preferably 0.1 or less, more preferably 0 or less. Specific examples of the electron-donating group include an alkyl group, an alkoxy group, an amine group, a urea group, an allyl group, a hydroxyl group and the like, and an amine group is preferred. The groups may also be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an alkoxy group, a thiol group, a thioalkoxy group, an amine group, a halogen atom or the like in a range in which electron donating is not lost. Replace. Further, the substituents may be further substituted by the substituents, and, if possible, may be bonded to each other to form a ring.

In the dye multimer of the present invention, the dye structure is preferably a dye structure represented by the formula (Ia). [化12] Ht represents a cationic heterocyclic ring containing two or more hetero atoms and one or more of the hetero atoms is a nitrogen atom, L represents a single bond, -N=N-, or an extended aryl group, B represents a substituent, and X represents an anion, Ht At least one of B, X and X has a bonding site with an atomic group constituting the dye multimer.

In the formula (Ia), the cationic heterocyclic ring represented by the above formula (I) is preferably a cationic heterocyclic ring represented by the above formula (1) to the formula (6). ring.

In the formula (Ia), L represents -N=N-, or an extended aryl group. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, particularly preferably from 6 to 10. The aryl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent.

In the formula (Ia), B represents a substituent. The substituent may be a group exemplified in the group of the substituent A described later, and an aryl group, a heterocyclic group and an amine group are preferred. Further, in the case where L represents an aryl group, B is preferably an electron-donating group, and more preferably an amine group. The amine group is preferably a dialkylamino group or a cyclic amino group. Specific examples thereof include a dimethylamino group, a diethylamino group, an N-hexahydropyridyl group, a morpholinyl group, and the like. Further, B is preferably substituted in the para position with respect to Ht. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, particularly preferably from 6 to 10. The aryl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. The heterocyclic group is preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members, and preferably has at least one ring-forming atom. a heterocyclic group of any one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Among them, an aromatic heterocyclic group of 5 or 6 members having a carbon number of 3 to 30 is preferred. The heterocyclic group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. Examples of the heterocyclic group include 2-furyl group, 2-thienyl group, 2-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, and 1-methyl-1H-fluorene. 3-yl, 2-indolyl, and the like. Among them, a 1-alkyl-1H-indol-3-yl group is preferred. The amine group includes a group represented by -N(R ¹¹⁰ )(R ¹¹¹ ). R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The hydrogen atom, the alkyl group, the aryl group and the heterocyclic group are exemplified. At least one of R ¹¹⁰ and R ¹¹¹ is preferably an alkyl group, and more preferably both of R ¹¹⁰ and R ¹¹¹ are an alkyl group. That is, the amine group is more preferably a dialkylamino group. In particular, in the case where L represents an aryl group, it is more preferred that both of R ¹¹⁰ and R ¹¹¹ are an alkyl group. Further, R ¹¹⁰ and R ^{111 are} also preferably bonded to form a ring. That is, the amine group is also preferably a cyclic amine group. In particular, in the case where both of R ¹¹⁰ and R ¹¹¹ are an alkyl group, it is also preferred that the two are bonded to each other to form a ring. In the case where R ¹¹⁰ and R ^{111 are} bonded to form a ring, R ¹¹⁰ and R ^{111 are} preferably selected from the group consisting of -O-, -NH-, -CH ₂ - and combinations thereof. The divalent linking groups are joined to form a ring. The divalent linking group is preferably -O- or -CH ₂ -.

In the formula (Ia), X represents an anion. The anion will be described later.

In the formula (Ia), at least one of Ht, B and X has a bonding site with an atomic group constituting the dye multimer, and preferably at least one of Ht and B has a bonding site with an atomic group constituting the dye multimer. More preferably, Ht has a bonding site with an atomic group constituting the dye multimer. In the dye multimer in which Ht is bonded to the atoms constituting the dye multimer, the effect of shielding the cation is particularly high, and the effect of the present invention is more remarkable.

In the dye multimer of the present invention, the dye structure is preferably a dye structure represented by the formula (Ia-1). [Chemistry 13] Y ^a represents a sulfur atom or -NR ^Ya -, Y ^b represents a nitrogen atom or -CR ^Yb -, and R ^a , R ^Ya and R ^Yb each independently represent a hydrogen atom or a substituent, and R ^a and R ^Ya and R ^a R ^Yb may also be bonded to form a ring, L represents -N=N-, or an extended aryl group, B represents a substituent, X represents an anion, and at least one of R ^a , R ^Ya , R ^Yb , X and B has A bonding site of an atomic group constituting a dye multimer.

L and B of the formula (Ia-1) have the same meanings as L and B of the formula (Ia). In the formula (Ia-1), Y ^a represents a sulfur atom or -NR ^Ya -, Y ^b represents a nitrogen atom or -CR ^Yb -, and R ^a , R ^Ya and R ^Yb each independently represent a hydrogen atom or a substituent. Examples of the substituent represented by R ^a , R ^Ya and R ^Yb include the substituents listed in the group of the substituent A described later. For example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc. are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. The alkyl group may be a straight chain, a branch or a ring, and is preferably a straight chain or a branched chain. The alkyl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be a straight chain, a branched chain or a cyclic chain, and is preferably a straight chain or a branched chain. The alkyl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, particularly preferably from 6 to 10. The aryl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. The heterocyclic group is preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members, and preferably has at least one ring-forming atom. a heterocyclic group of any one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom.

In the formula (Ia-1), R ^a and R ^Ya and R ^a and R ^Yb may be bonded to each other to form a ring. The ring may be a single ring or a multiple ring. The ring is preferably an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, and a thiazole ring. , imidazole ring, pyrazole ring, anthracene ring, indazole ring and the like. The aromatic ring is preferably a hydrocarbon aromatic ring, more preferably a benzene ring.

In the formula (Ia-1), at least one of R ^a , R ^Ya , R ^Yb , X and B has a bonding site with an atomic group constituting the dye multimer, preferably R ^a , R ^Ya , R ^Yb and B At least one of the bonding sites having an atomic group constituting the dye multimer, more preferably at least one of R ^a , R ^Ya and R ^Yb has a bonding site with an atomic group constituting the dye multimer.

In the present invention, the dye multimer preferably has a dye structure represented by the formula (I-1) or a dye structure represented by the formula (I-2).

[Chemistry 14] In the formula (I-1), R ¹ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ and R ⁹ to R ^{1 2} each independently represent a hydrogen atom or a substituent. a group, Y ¹ represents a sulfur atom or -NR ^{Y 1} -, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ to R ² , R ⁷ to R ^{1 2} , R ^Y1 and At least one of X has a bonding site with an atomic group constituting the dye multimer.

[化15] In the formula (I-2), R ^{1 01} , R ^{11 0} and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^{1 02} to R ^{1 05} , R ^{1 06} to R ^{1 09} Each independently represents a hydrogen atom or a substituent, and R ^{11 0} and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or -NR ^{Y 2} -, and R ^{Y 2} represents a hydrogen atom, an alkyl group, an aryl group or a hetero atom. The ring group, X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^{Y 2} and X has a bonding site with an atomic group constituting the dye multimer.

In the formula (I-1), R ¹ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. The alkyl group may be a straight chain, a branch or a ring, and is preferably a straight chain or a branched chain. The alkyl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, particularly preferably from 6 to 10. The aryl group may have a substituent or may be unsubstituted. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. The heterocyclic group is preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members, and preferably has at least one ring-forming atom. a heterocyclic group of any one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom.

In the formula (I-1), Y ¹ represents a sulfur atom or -NR ^{Y 1} -. R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, the aryl group and the heterocyclic group represented by R ^Y1 have the same meanings as the alkyl group, the aryl group and the heterocyclic group described in R ¹ and R ⁸ , and the preferred ranges are also the same.

In the formula (I-1), R ² , R ⁷ and R ⁹ to R ^{1 2} each independently represent a hydrogen atom or a substituent. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. For example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc. are mentioned. The preferred range of the halogen atom, the alkyl group, the alkenyl group, the aryl group and the heterocyclic group has the same meaning as the range described in the formula (Ia-1).

In the formula (I-2), R ¹⁰¹ , R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹¹⁰ and R ¹¹¹ may also be bonded to form a ring. R ^{101 is} preferably a hydrogen atom, an alkyl group or an aryl group. R ¹¹⁰ and R ¹¹¹ are each independently a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably an alkyl group. In the case where R ¹¹⁰ and R ^{111 are} bonded to form a ring, R ¹¹⁰ and R ^{111 are} preferably selected from the group consisting of -O-, -NH-, -CH ₂ - and combinations thereof. The divalent linking groups are joined to form a ring. The divalent linking group is preferably -O- or -CH ₂ -. The alkyl group, the aryl group and the heterocyclic group represented by R ¹⁰¹ , R ¹¹⁰ and R ¹¹¹ have the same meanings as the alkyl group, the aryl group and the heterocyclic group described in R ¹ and R ⁸ of the formula (I-1). The range is also the same.

In the formula (I-2), R ¹⁰² to R ¹⁰⁵ and R ¹⁰⁶ to R ¹⁰⁹ each independently represent a hydrogen atom or a substituent. The substituent which is mentioned in the group of the substituent A mentioned later is mentioned as a substituent. For example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc. are mentioned. The preferred range of the halogen atom, the alkyl group, the alkenyl group, the aryl group and the heterocyclic group has the same meaning as the range described in the formula (Ia-1).

In the formula (I-2), Y ² represents a sulfur atom or -NR ^{Y 2} -. R ^Y2 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, the aryl group and the heterocyclic group represented by R ^Y2 have the same meanings as the alkyl group, the aryl group and the heterocyclic group described in R ¹ and R ⁸ of the formula (I-1), and the preferred ranges are also the same.

In the formula (I-1) and the formula (I-2), X represents an anion. The anion may be an organic anion or an inorganic anion, preferably an organic anion. Examples of the anion include a fluorine anion, a chloride anion, a bromine anion, an iodine anion, a cyanide anion, a perchlorate anion, and a non-nucleophilic anion. From the viewpoint of heat resistance, an anion which is not nucleophilic is preferred. Examples of the anion include a known non-nucleophilic anion described in Paragraph No. 0075 of JP-A-2007-310315, which is incorporated herein by reference. Here, the term "non-nucleophilic" refers to a property of not nucleophilic attack on a pigment by heating.

The anion is preferably an anthracene anion (for example, a bis(sulfonyl) quinone anion), a tris(sulfonyl)methyl anion, an anion having a boron atom, more preferably a bis(sulfonyl) quinone imine. An anion and a tris(sulfonyl)methyl anion, and more preferably an bis(sulfonyl) quinone imine. By using such an anion, there is a tendency that the effects of the present invention are more effectively exhibited.

The quinone imine anion is preferably a structure represented by the following formula (AN-1). [Chemistry 16] In the formula (AN-1), X ¹ and X ² each independently represent a halogen atom, an alkyl group or an aryl group. X ¹ and X ² may also be bonded to each other to form a ring. Y ¹ and Y ² each independently represent -SO ₂ - or -CO-.

X ¹ and X ² are each independently a fluorine atom or a C 1-10 alkyl group having a fluorine atom or a C 6-10 aryl group, more preferably a C 1-10 perfluoroalkyl group. Further, it is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a trifluoromethyl group. Preferably, Y ¹ and Y ² represent at least one of -SO ₂ -, more preferably -SO ₂ -.

The tris(sulfonyl)methyl anion is preferably a structure of the following formula (AN-2). [化17] In the formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a halogen atom or an alkyl group. The alkyl group represented by X ³ , X ⁴ and X ⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group may be an unsubstituted alkyl group or may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom. X ³ , X ⁴ and X ⁵ are each preferably a fluorine atom or an alkyl group having a fluorine atom, and more preferably an alkyl group having a fluorine atom. The alkyl group having a fluorine atom is preferably a C 1-10 alkyl group having a fluorine atom, more preferably a C 1-10 perfluoroalkyl group, and still more preferably a C 1-4 perfluoroalkyl group. Particularly preferred is trifluoromethyl.

Examples of the anion having a boron atom include a tetrafluoroborate anion, a tetraphenylborate anion, and a tetra-perfluorophenylborate anion.

The non-nucleophilic anion may further have a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated bond (for example, a vinyl group, an allyl group, a styryl group, a (meth)acrylonitrile group), or an epoxy group or an oxetanyl group. A group having a cyclic ether structure, or a hydroxymethyl group or the like.

The molecular weight of the anion is preferably from 100 to 1,000, more preferably from 200 to 500.

Specific examples of the anion are shown below, but the present invention is not limited thereto. In the case where the anion has a bonding site with an atomic group constituting the dye multimer, a portion obtained by removing one or more atoms from the structural formula shown in the following specific examples becomes a constituent of the dye multimer. The bonding site of the atomic group.

[化18]

In the formula (I-1), at least one of R ¹ , R ² , R ⁷ to R ¹² , R ^{Y 1} and X has a bonding site with an atomic group constituting the dye multimer, preferably R ¹ and R ^{2 .} At least one of R ⁷ to R ¹² and R ^{Y 1} has a bonding site with an atomic group constituting the dye multimer, and more preferably at least one of R ¹ , R ² and R ^{Y 1} has a composition with a dye multimer. The bonding site of the atomic group.

In the formula (I-2), at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^{Y 2} and X has a bonding site with an atomic group constituting the dye multimer, and preferably at least R ¹⁰¹ to R ¹⁰⁹ and R ^{Y 2} . One of the bonding sites having an atomic group constituting the dye multimer, more preferably at least one of R ¹⁰¹ to R ¹⁰⁵ and R ^{Y 2} has a bonding site with an atomic group constituting the dye multimer.

(Substituent Group A) Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, and an aryloxy group. , decyloxy, heterocyclic oxy, decyloxy, amine methyl methoxy, alkoxycarbonyloxy, amine (including alkylamino, anilino), decylamino, aminocarbonylamino , alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocycle Thio, sulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, Aminomethyl hydrazino, aryl azo or heterocyclic azo, quinone imine, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, decylalkyl and the like. The details will be described below. The halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group (a linear, branched or cyclic substituted or unsubstituted alkyl group, preferably having a carbon number of 1 to 30) The alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group or a ring. Hexyl, cyclopentyl. The cyclic alkyl group may also be a polycyclic alkyl group, such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, such as bicyclo [1, 2, 2] a polycyclic structure group such as heptan-2-yl, bicyclo[2,2,2]oct-3-yl) or tricycloalkyl. The cyclic alkyl group is preferably a monocyclic cycloalkyl group, a bicycloalkyl group, particularly preferably a monocyclic cycloalkyl group; an alkenyl group (a linear, branched or cyclic substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, for example Listed: vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl. cyclic alkene The group is also preferably a polycycloalkenyl group such as a bicycloalkenyl group (preferably having a carbon number of 5 to 30) Alken or unsubstituted bicycloalkenyl, for example bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl) or tricyclic Alkenyl. Cyclic alkenyl is particularly preferably a monocyclic cycloalkenyl); alkynyl (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, tri Methyl decyl ethynyl); aryl (preferably substituted or unsubstituted aryl having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecane) a mercaptoaminophenyl); a heterocyclic group (preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group of 5 to 7 members, Further, it is preferably a heterocyclic group having at least one carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom in the ring-forming atom, and is a 5-membered or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. (heteroaryl)); cyano; hydroxy; nitro; carboxy (hydrogen atom dissociable (ie carbonate)), which may be in the form of a salt (eg, sodium, potassium, magnesium, calcium, Iron salt, aluminum salt, etc.), alkyl ammonium salt ( Ammonium salts of long chain monoalkylamines such as octylamine, laurylamine, stearylamine, palmitoyltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. Alkyl ammonium salt), etc.); alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, third Butoxy, n-octyloxy, 2-methoxyethoxy); aryloxy (preferably substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, such as phenoxy, 2- Methylphenoxy, 2,4-di-p-pentylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylideneaminophenoxy a decyloxy group (preferably a decyloxy group having a carbon number of 3 to 20, such as a trimethyldecyloxy group, a tert-butyldimethylsilyloxy group); a heterocyclic oxy group (preferably a carbon number of 2) The substituted or unsubstituted heterocyclic oxy group of ～30, preferably the heterocyclic moiety described in the heterocyclic group, for example, 1-phenyltetrazole-5-oxyl, 2- Tetrahydropyranyloxy); decyloxy (preferably substituted or unsubstituted alkylcarbonyl having 2 to 30 carbon atoms) Oxyl group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as methyl methoxy, ethoxylated, trimethyl ethoxylated, stearyloxy, benzamidine Oxyl, p-methoxyphenylcarbonyloxy); amine methyl methoxy (preferably substituted or unsubstituted amine methyl carbonyl having 1 to 30 carbon atoms, such as N,N-dimethyl Aminomethyl methoxy, N,N-diethylamine methyl methoxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylamine methoxycarbonyl Alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, ethoxycarbonyloxy group, third butyl group) An oxycarbonyloxy group, an n-octylcarbonyloxy group; an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy) Alkyl, p-methoxyphenoxycarbonyloxy, n-hexadecyloxyphenoxycarbonyloxy); an amine group (containing an alkylamino group, an arylamino group, and a heteroarylamino group). Preferred are an amine group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a heteroaryl having 0 to 30 carbon atoms. Amino group, for example, an amine group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, an N-1,3,5-triazin-2-yl group Amidino) (preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, For example, mercaptoamine, etidylamino, trimethylethenylamine, laurylamine, benzhydrylamine, 3,4,5-tri-n-octyloxyphenylcarbonyl Aminocarbonyl); preferably substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, an aminomethylamino group, N,N-dimethylaminocarbonyl group Amino, N,N-diethylaminocarbonylamino, morpholinylcarbonylamino); alkoxycarbonylamino (preferably a substituted or unsubstituted alkoxy group having 2 to 30 carbon atoms) A carbonylamino group such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonylamine , an octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group; an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxy group having 7 to 30 carbon atoms; a carbonylamino group, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, a m-octyloxyphenoxycarbonylamino group; an aminesulfonylamino group (preferably having a carbon number of 0 to 30) Substituted or unsubstituted amine sulfonylamino group, such as sulfonylamino, N,N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino) An alkylsulfonylamino group or an arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted carbon number of 6 to 30 or Unsubstituted arylsulfonylamino group, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonyl Amino, p-methylphenylsulfonylamino); fluorenyl; alkylthio (preferably substituted or unsubstituted alkylthio having 1 to 30 carbon atoms, such as methylthio, ethylthio, N-hexadecanethio); arylthio (preferably substituted by carbon number 6 to 30 or Unsubstituted arylthio group, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio); heterocyclic thio (preferably substituted or unsubstituted carbon having 2 to 30 carbon atoms) The cyclothio group, preferably having a heterocyclic moiety as defined in the heterocyclic group, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio; (preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, such as N-ethylaminesulfonyl, N-(3-dodecyloxypropyl)aminesulfonyl, N,N-Dimethylamine sulfonyl, N-acetyl sulfonyl sulfonyl, N-benzylidene sulfonyl sulfonyl, N-(N'-phenylamine carbaryl) sulfonyl sulfonyl a sulfo group (a hydrogen atom can be dissociated (ie, a sulfonate group), which can be in the form of a salt (a metal salt (eg, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, an iron salt, an aluminum salt, etc.), an alkyl ammonium salt) a salt (for example, an ammonium salt of a long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmitoyltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt Or a quaternary alkyl ammonium salt), etc.); an alkylsulfinyl group or an arylsulfinyl group (preferably a carbon number of 1 to 30) Substituted or unsubstituted alkylsulfinyl, 6 to 30 substituted or unsubstituted arylsulfinylene, such as methylsulfinyl, ethylsulfinyl, phenylsulfin Anthracenyl, p-methylphenylsulfinyl); alkylsulfonyl or arylsulfonyl (preferably substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms, 6 to a substituted or unsubstituted arylsulfonyl group of 30, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl); a mercapto group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an ethyl fluorenyl group, a trimethyl ethane group, 2-chloroethyl group, stearyl group, benzhydryl group, p-octyloxyphenylcarbonyl); aryloxycarbonyl group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) a carbonyl group, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group; an alkoxycarbonyl group (preferably a carbon number of 2 to 30) Substituted or unsubstituted alkoxycarbonyl , for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl); aminemethanyl (preferably substituted or unsubstituted amine having 1 to 30 carbon atoms) Mercapto group, for example, anthracene, N-methylamine, fluorenyl, N,N-dimethylamine, fluorenyl, N,N-di-n-octylamine, fluorenyl, N-(methyl Sulfhydryl)aminomethane); arylazo or heterocyclic azo (preferably substituted or unsubstituted arylazo having 6 to 30 carbon atoms, carbon number 3 to 30) a substituted or unsubstituted heterocyclic azo group (the heterocyclic moiety is preferably a heterocyclic moiety described in the above heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylsulfide Base-1,3,4-thiadiazol-2-ylazo); quinone imine (preferably a substituted or unsubstituted quinone group having 2 to 30 carbon atoms, such as N-butadiene) a phosphinium group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methyl phenoxyphosphino group; a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example) a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group; a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example Diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy); phosphinylamino (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example Dimethoxy phosphinylamino, dimethylaminophosphinylamino) decyl (preferably a substituted or unsubstituted decyl group having a carbon number of 3 to 30, such as trimethyldecyl , tert-butyldimethylmethylalkyl, phenyldimethylalkylalkyl). These may further have a substituent based on a further further group which may be substituted. As a further substituent, the group described in the group of the substituent A can be mentioned.

<<Preferred Aspect of Pigment Multimer>> In the present invention, the dye multimer preferably has a structure in which two or more dye structures are bonded to a divalent or higher linking group. The dye multimer preferably has at least one selected from the group consisting of a repeating unit having a dye structure in a side chain and a repeating unit having a dye structure in the main chain.

Further, the dye multimer preferably contains at least one of a repeating unit represented by the following formula (A) and a repeating unit represented by the formula (C), or is represented by the following formula (D). That is, the dye multimer is preferably a dye multimer (also referred to as a dye multimer (A)) having a repeating unit represented by the formula (A), and a pigment having a repeating unit represented by the formula (C). A polymer (also referred to as a dye multimer (C)) and a polymer represented by formula (D) (also referred to as a dye multimer (D)).

<<<Pigment Multimer (A)>>> The dye multimer (A) preferably contains a repeating unit represented by the formula (A). In the dye multimer (A), the proportion of the repeating unit represented by the formula (A) is preferably from 10% by mass to 100% by mass based on all the repeating units constituting the dye multimer. The lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less. [Chemistry 19] In the formula (A), A ¹ represents a main chain of a repeating unit, L ¹ represents a single bond or a divalent linking group, and DyeI represents an azo group or an aromatic ring group bonded to a hetero atom containing two or more hetero atoms. A dye structure having a structure in which one or more of the cationic heterocyclic rings are nitrogen atoms.

In the formula (A), A ¹ represents the main chain of the repeating unit. Linking groups A ¹ include the like formed by the polymerization reaction, is preferably derived from a (meth) acrylic group, styrene group backbone of the compound, a vinyl ether group. Further, the aspect in which the main chain has a cyclic alkyl group is also preferable. A ¹ as long as the linking group according to a known polymerizable monomers can be formed, is not particularly limited. A ^{1 is} preferably a linking group represented by the following (XX-1) to (XX-25), and more preferably selected from the group consisting of (XX-1), (XX-2), (XX-10) to (XX-). 17), (XX-18), (XX-19), (XX-24) and (XX-25), and further preferably selected from (XX-1), (XX-2), (XX-10) ~(XX-17), (XX-24) and (XX-25).

In the following formula, * is a bonding site with L ¹ of the formula (A). Me represents a methyl group. Further, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

[Chemistry 20]

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, -S-, and -C. (=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ - and a linking group formed by linking two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

The carbon number of the alkylene group is preferably from 1 to 30. The upper limit is preferably 25 or less, and further preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkylene group may be any of a straight chain, a branched chain, and a cyclic chain. The alkylene group may have a substituent or may be unsubstituted. The substituent described in the group of the substituent A can be mentioned as a substituent. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent described in the group of the substituent A can be mentioned as a substituent. The heterocyclic linking group is preferably a 5-membered ring or a 6-membered ring. The hetero atom of the heterocyclic linking group is preferably an oxygen atom, a nitrogen atom or a sulfur atom. The number of the hetero atoms in the heterocyclic linking group is preferably from one to three. The heterocyclic linking group may have a substituent or may be unsubstituted. The substituent described in the group of the substituent A can be mentioned as a substituent.

DyeI represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic hetero ring containing two or more hetero atoms and one or more hetero atoms are nitrogen atoms. The dye structure is preferably a structure in which one or more arbitrary atoms are removed from a cation or an anion of a dye compound having a cation and an anion, and the cation contains a pigment skeleton having the cationic heterocyclic ring, and more preferably is removed from the cation. A structure made up of more than one arbitrary atom. That is, in the present invention, in the dye structure represented by DyeI, the cation may be bonded to A ¹ or L ^{1 of the} formula (A), or may be an anion and an A ¹ or L ¹ bond of the formula (A). Preferably, the cation is bonded to A ¹ or L ^{1 of} formula (A). Specifically, the repeating unit represented by the formula (A) includes a repeating unit represented by the formula (A-1) and a repeating unit represented by the formula (A-2), and is preferably represented by the formula (A-1). Repeat unit. According to this aspect, the cationic portion of the dye structure is easily blocked by the polymer chain, and aggregation of the dye multimer can be suppressed, and a more excellent effect can be easily obtained.

[Chem. 21] In the formula, A ¹ represents a main chain of a repeating unit, and L ^1a and L ^1b each independently represent a single bond or a divalent linking group, and DyeI-1 and DyeI-2 each independently represent a hetero atom having two or more hetero atoms. A cation of a cationic heterocyclic ring in which one or more of the atoms is a nitrogen atom, and X1 and X2 each independently represent an anion.

In the formula (A-1), the divalent linking group represented by L ^1a includes a divalent linking group described in L ¹ of the formula (A). L ^{1a is} preferably a single bond, or an alkyl group, an aryl group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of two or more of these. The linking group formed is more preferably a single bond, or an alkylene group, an extended aryl group, and a divalent group which is a combination of one or more selected from the group consisting of -O-, -COO-, and -OCO-.

In the formula (A-1), the cation represented by DyeI-1 is preferably a cation of the dye structure of the formula (I-1) and the formula (I-2). Further, the anion represented by X1 is preferably an anion described in the dye structure.

In the formula (A-2), the divalent linking group represented by L ^1b includes a divalent linking group described in L ¹ of the formula (A). L ^{1b is} preferably a single bond, or an alkyl group, an aryl group, -NH-, -CO-, -O-, -COO-, -OCO-, -SO ₂ - and combinations of two or more of these The linking group to be formed is preferably an alkyl group, -O- or -SO ₂ -, and a linking group in which two or more of these are combined. Further, the alkylene group and the extended aryl group are also preferably substituted. The substituent is preferably an electron-donating group, and examples thereof include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a nitro group, a cyano group, a halogenated alkyl group (for example, a trifluoromethyl group), a halogenated aryl group, and the like. .

In the formula (A-2), the cation represented by DyeI-2 is preferably a cation of the dye structure of the formula (I-1) and the formula (I-2). Further, the anion represented by X2 is preferably an anion described in the dye structure. Specific examples of the repeating unit represented by the formula (A-2) include the structures described in Paragraph No. 0162 to Paragraph No. 0166 of JP-A-2014-199436.

The dye multimer comprising a repeating unit represented by the formula (A) can be synthesized by (1) a method of synthesizing a dye compound having a polymerizable group by addition polymerization; (2) by having a polymer having a highly reactive functional group such as an isocyanate group, an acid anhydride group or an epoxy group, and a dye compound having a functional group (hydroxyl group, primary amino group or secondary amine group, carboxyl group, etc.) capable of reacting with a highly reactive group The method of reaction. The addition polymerization can be carried out by a known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization), wherein the synthesis is carried out especially by radical polymerization to make the reaction conditions mild, and the pigment skeleton is not decomposed, so that it is preferred. . Well-known reaction conditions can be applied to the radical polymerization. From the viewpoint of heat resistance, the dye multimer having a repeating unit represented by the formula (A) is preferably a radical polymer obtained by radical polymerization using a dye compound having an ethylenically unsaturated bond.

Specific examples of the repeating unit represented by the formula (A) include the followings. In the following structural formula, Me is a methyl group and Et is an ethyl group. [化22] [化23] [Chem. 24] [化25]

Specific examples of the repeating unit represented by the formula (A-2) include the followings. [Chem. 26]

(Other Repeating Unit) The dye multimer of the present invention may contain other repeating units in addition to the repeating unit represented by the formula (A). Other repeating units may also include a functional group such as a curable group or an acid group. It may also contain no functional groups. The dye multimer preferably has one or more selected from the group consisting of a repeating unit having an acid group and a repeating unit having a curable group.

Examples of the curable group include a radical polymerizable group, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a hydroxymethyl group. Examples of the radical polymerizable group include a group containing an ethylenically unsaturated bond such as a vinyl group, a (meth)allyl group or a (meth)acryloyl group. The curable group is preferably a radical polymerizable group. The proportion of the repeating unit having a curable group is preferably from 0% by mass to 50% by mass based on all the repeating units constituting the dye multimer. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.

The acid group may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. The acid group may be contained alone or in combination of two or more. The proportion of the repeating unit having an acid group is preferably from 0% by mass to 50% by mass based on all the repeating units constituting the dye multimer. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.

Examples of the other functional group include a repeating group of 2 to 20 unsubstituted alkylene oxide chains, a development promoting group such as a lactone, an acid anhydride, a guanamine or a cyano group, a long-chain alkyl group and a ring. A hydrophilicity adjusting group such as an alkyl group, an aralkyl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimine group or an amine group can be appropriately introduced. In the repeating group containing 2 to 20 unsubstituted alkylene oxide chains, the number of repeating alkoxy groups is preferably from 2 to 15, more preferably from 2 to 10. An alkylene oxide chain is represented by -(CH ₂ ) _n O-, n is an integer, and n is preferably from 1 to 10, more preferably from 1 to 5, still more preferably 2 or 3.

Specific examples of other repeating units are shown, but the present invention is not limited to these. [化27] [化28]

<<<Pigment Multimer (C)>>> The dye multimer (C) preferably contains a repeating unit represented by the formula (C). In the dye multimer (C), the proportion of the repeating unit represented by the formula (C) is preferably from 10% by mass to 100% by mass based on all the repeating units constituting the dye multimer. The lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less. [化29] In the formula (C), L ³ represents a single bond or a divalent linking group, and DyeIII represents a cationic group having an azo group or an aromatic ring group bonded to one or more hetero atoms including two or more hetero atoms and a hetero atom. A dye structure of a heterocyclic structure, m represents 0 or 1.

In the formula (C), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, -S-, and -C. (=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ - and a linking group formed by linking two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The alkyl group and the alkylene group preferably have 1 to 30 carbon atoms. The upper limit is preferably 25 or less, and further preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkyl group and the alkylene group may be any of a straight chain, a branched chain, and a cyclic group. The carbon number of the aryl group and the aryl group is preferably from 6 to 20, more preferably from 6 to 12. The heterocyclic linking group and the heterocyclic group are preferably a 5-membered ring or a 6-membered ring. The hetero atom of the heterocyclic linking group and the heterocyclic group is preferably an oxygen atom, a nitrogen atom or a sulfur atom. The number of the hetero atoms in the heterocyclic linking group and the heterocyclic group is preferably from one to three. The alkylene group, the extended aryl group, the heterocyclic linking group, the alkyl group, the aryl group, and the heterocyclic group may be unsubstituted or may have a substituent. Examples of the substituent include a curable group and an acid group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a hydroxymethyl group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. The acid group may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. Further, it may have a repeating group containing 2 to 20 unsubstituted alkylene oxide chains, a lactone, an acid anhydride, a guanamine, a cyano group or the like, a development promoting group, a long-chain alkyl group, and a cyclic alkyl group. A hydrophilic or hydrophobicity adjusting group such as an aralkyl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group or an amine group is used as a substituent.

L ^{3 is} preferably an alkyl group, an aryl group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, and a linking group of two or more of these. . DyeIII represents a dye structure having a structure in which an azo group or an aromatic ring group is bonded to a cationic hetero ring containing two or more hetero atoms and one or more hetero atoms are nitrogen atoms. The dye structure is preferably a structure in which one or more arbitrary atoms are removed from a cation or an anion of a dye compound having a cation and an anion, and the cation contains a pigment skeleton having the cationic heterocyclic ring, and more preferably is removed from the cation. A structure made up of more than one arbitrary atom. m represents 0 or 1, preferably 1.

The dye multimer having a constituent unit represented by the formula (C) can be synthesized by sequential polymerization. The sequential polymerization may, for example, be a complex addition (for example, a reaction of a diisocyanate compound with a diol, a reaction of a diepoxy compound with a dicarboxylic acid, a reaction of a tetracarboxylic dianhydride with a diol, etc.) and polycondensation (for example, two). Reaction of a carboxylic acid with a diol, reaction of a dicarboxylic acid with a diamine, etc.). Among them, in particular, the synthesis is carried out by a complex addition reaction, whereby the reaction conditions are mild, and the dye structure is not decomposed, which is preferable. Well-known reaction conditions can be applied in successive polymerizations.

Specific examples of the repeating unit represented by the formula (C) include the followings. [化30]

The dye multimer (C) may contain other repeating units described in the dye multimer (A) in addition to the repeating unit represented by the formula (C).

<<<Pigment Multimer (D)>>> The dye multimer (D) is preferably represented by the formula (D). [化31] In the formula (D), L ⁴ represents a (n+k)-valent linking group, n represents an integer of 2 to 20, k represents an integer of 0 to 20, and DyeIV represents an azo group or an aromatic ring-based bond to be contained. a dye structure having a structure in which two or more hetero atoms and one or more hetero atoms are a cationic hetero ring of a nitrogen atom, and P represents a substituent. When n is 2 or more, a plurality of DyeIVs may be different from each other. When k is 2 or more, a plurality of Ps may be different from each other, and n+k represents an integer of 2 to 20.

In the formula (D), n is preferably from 2 to 15, more preferably from 2 to 14, more preferably from 2 to 8, particularly preferably from 2 to 7, particularly preferably from 2 to 6. The total of n and k is 2 to 20, preferably 2 to 15, more preferably 2 to 14, still more preferably 2 to 8, particularly preferably 2 to 7, most preferably 2 to 6. Further, n and k in one dye multimer are integers, and in the present invention, a plurality of dye multimers having different n and k in the formula (D) may be contained. Therefore, the average value of n and k in the coloring composition of the present invention is not an integer.

The (n+k)-valent linking group includes one to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 The base of a sulfur atom. Specific examples of the (n+k)-valent linking group include the following structural units or a combination of two or more structural units (a ring structure can be formed).

[化32]

Specific examples of the (n+k)-valent linking group are shown below. However, the present invention is not limited to these. In addition, the linking group described in Paragraph No. 0071 to Paragraph No. 0072 of JP-A-2008-222950, and the linking group described in Paragraph No. 0176 of JP-A-2013-029760.

In the formula (D), P represents a substituent. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a hydroxymethyl group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Further, the substituent represented by P may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P's may be the same or different. In the case where P is a monovalent polymer chain having a repeating unit and k is 1, P preferably has 2 to 20 (preferably 2 to 15, more preferably 2 to 10) sources. A monovalent polymer chain from a repeating unit of a vinyl compound. Further, when P is a monovalent polymer chain having a repeating unit and k is 2 or more, the average value of the number of repeating units derived from the vinyl compound of k P is preferably 2 to 20 ( It is preferably 2 to 15 and further preferably 2 to 10). When P is a monovalent polymer chain having a repeating unit, the average of the number of repeating units of P when k is 1, and the number of repeating units of k of P when k is 2 or more can be obtained by NMR (Nuclear Magnetic Resonance, NMR) was used to determine.

In the case where P is a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P include other repeating units described in the dye multimer (A). The other repeating unit preferably has one or more selected from the group consisting of the repeating unit having an acid group and the repeating unit having a curable group. In the case of including a repeating unit having an acid group, developability can be improved. In the case of including a repeating unit having a curable group, solvent resistance can be further improved. In the case where P contains a repeating unit containing an acid group, the proportion of the repeating unit containing an acid group is preferably from 10 mol% to 80 mol%, more preferably 10 mol%, based on all repeating units of P. 65 moles %. In the case where P contains a repeating unit having a hardening group, the proportion of the repeating unit having a hardening group is preferably from 10 mol% to 80 mol%, more preferably 10 mol%, with respect to all repeating units of P. %~65% by mole. Color inhomogeneity can be further optimized by including a repeating unit having a curable group.

In the formula (D), DyeIV represents a pigment structure. The dye structure represented by DyeIV is preferably a structure obtained by removing one or more arbitrary atoms from a cation or an anion of a dye compound having a cation and an anion, and the cation contains a pigment skeleton having the cationic heterocyclic ring, more preferably A structure formed by removing one or more arbitrary atoms from a cation. That is, in the present invention, the dye structure represented by DyeIV is preferably an L ⁴ bond of the cation with the formula (D).

In addition, the dye structure represented by DyeIV may be one in which one or more atoms of the dye compound are removed, and a part of the dye compound is bonded to L ⁴ or may be contained in the main chain or the side chain. A polymer chain of a repeating unit having a structure (a structure in which one or more atoms of a dye compound are removed). The polymer chain is not particularly limited as long as it contains a dye structure, and is preferably one selected from the group consisting of a (meth)acrylic resin, a styrene resin, and a (meth)acrylic acid/styrene resin. The repeating unit of the polymer chain is not particularly limited, and examples thereof include a repeating unit represented by the formula (A), a repeating unit represented by the formula (C), and the like. Further, the total of the repeating units having a dye structure among all the repeating units constituting the polymer chain is preferably from 5 mol% to 60 mol%, more preferably from 10 mol% to 50 mol%, and still more preferably 20 Mole% to 40% by mole. The polymer chain may contain other repeating units described in the dye multimer (A) in addition to the repeating unit having a dye structure. It is preferred to have one or more selected from the group consisting of a repeating unit having an acid group and a repeating unit having a curable group as another repeating unit. In the case where the polymer chain comprises a repeating unit having a hardening group, the ratio of the repeating unit having a hardening group is preferably, for example, 5 to 50 moles per 100 repeating units of the polymer chain. Ears, more preferably 10 moles to 40 moles. In the case where the polymer chain comprises a repeating unit having an acid group, the proportion of the repeating unit having an acid group is preferably, for example, 5 to 50 m, relative to 100 ppm of all repeating units of the polymer chain. More preferably 10 moles to 40 moles.

The dye multimer represented by the formula (D) can be synthesized by the following method or the like. (1) A compound obtained by introducing a functional group selected from a carboxyl group, a hydroxyl group, an amine group or the like into a terminal, a hydrazine halide having a dye structure, an alkyl halide having a dye structure, or an isocyanate having a dye structure; The method of reaction. (2) A method of subjecting a compound having a carbon-carbon double bond to a terminal to a Michael addition reaction with a thiol compound having a dye structure. (3) A method of reacting a compound having a carbon-carbon double bond introduced at its end with a thiol compound having a dye structure in the presence of a radical generator. (4) A method of reacting a polyfunctional thiol compound having a plurality of thiol groups introduced into a terminal with a compound having a carbon-carbon double bond and a dye structure in the presence of a radical generator. (5) A method of radically polymerizing a vinyl compound in the presence of a thiol compound having a dye structure.

The dye multimer (D) is preferably a structure represented by the formula (D-1). (D ^{1 -} L ⁴² ) _{n -} L ⁴ - (L ^{41 -} P ¹ ) _k (D-1) In the formula (D-1), L ⁴ represents a (n+k)-valent linking group. n represents an integer of 2 to 20, and k represents an integer of 0 to 20. D ¹ represents a dye structure, and P ¹ represents a substituent. When n is 2 or more, a plurality of D ¹ may be different from each other, and when k is 2 or more, a plurality of P ¹ may be different from each other. n+k represents an integer of 2-20.

Formula (D-1) in, L ^4, L ^4, n, and n-k and k are the same meaning as in formula (D), and preferred ranges are also the same.

In the formula (D-1), L ⁴¹ and L ⁴² each independently represent a single bond or a divalent linking group. When there are a plurality of L ⁴¹ and L ⁴² , they may be the same or different. The divalent linking group includes a group containing 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. It may be unsubstituted and may further have a substituent.

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

[化33]

Formula (D-1) in, P ¹ represents a substituent group. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a hydroxymethyl group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Further, the substituent represented by P ¹ may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. In the case where k is 2 or more, k P ^{1 's} may be the same or different. In the case where P ¹ is a monovalent polymer chain having a repeating unit and k is 1, P ¹ preferably has 2 to 20 (preferably 2 to 15 and further preferably 2 to 10). a monovalent polymer chain derived from a repeating unit of a vinyl compound. Further, when P ¹ is a monovalent polymer chain having a repeating unit and k is 2 or more, the average value of the number of repeating units derived from the vinyl compound of k P ¹ is preferably 2 to 20 One (preferably 2 to 15 and further preferably 2 to 10).

In the case where P ¹ represents a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P ¹ include other repeating units described in the dye multimer (A). The other repeating unit preferably has one or more selected from the group consisting of the repeating unit having an acid group and the repeating unit having a curable group. In the case where P ¹ comprising a repeating unit containing an acid group with respect to all repeating units P ^1, the ratio of the repeating units containing an acid group is preferably 10 mole% to 80 mole%, more preferably 10 molar %~65% by mole. In the case where P ¹ comprising repeating units having a curable group, with respect to all repeating units P ^1, with curable groups of the repeating unit is preferably 10 mole% to 80 mole%, more preferably 10 Mole% ~ 65 mol%.

In the formula (D-1), D ¹ represents a dye structure. The dye structure represented by D ¹ may be a polymer chain in which a part of the dye compound is bonded to L ⁴² or a repeating unit having a dye structure in a main chain or a side chain. The polymer chain is not particularly limited as long as it contains a dye structure, and is preferably one selected from the group consisting of a (meth)acrylic resin, a styrene resin, and a (meth)acrylic acid/styrene resin. The repeating unit of the polymer chain is not particularly limited, and examples thereof include a repeating unit represented by the formula (A), a repeating unit represented by the formula (C), and the like. Further, the total of the repeating units having a dye structure among all the repeating units constituting the polymer chain is preferably from 5 mol% to 60 mol%, more preferably from 10 mol% to 50 mol%, and still more preferably 20 Mole% to 40% by mole. The polymer chain may contain other repeating units described in the dye multimer (A) in addition to the repeating unit having a dye structure. It is preferred to have one or more selected from the group consisting of a repeating unit having an acid group and a repeating unit having a curable group as another repeating unit.

The dye multimer (D) is preferably a structure represented by the formula (D-2). (D ² -SC ¹ -B ¹ ) _n -L ⁴ -(B ² -C ² -SP ² ) _k (D-2) In the formula (D-2), L ⁴ represents (n+k) The link of the price. n represents an integer of 2 to 20, and k represents an integer of 0 to 20. D ² represents a dye structure, and P ² represents a substituent. B ¹ and B ² each independently represent a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-. R represents a hydrogen atom, an alkyl group or an aryl group. C ¹ and C ² each independently represent a single bond or a divalent linking group. S represents a sulfur atom. When n is 2 or more, a plurality of D ² may be different from each other, and when k is 2 or more, a plurality of P ² may be different from each other. n+k represents an integer of 2-20.

In the formula ^{(D-2), L 4} , L 4, n and k are the same meanings as n, and k in the formula (D), and preferred ranges are also the same.

In the formula (D-2), B ¹ and B ² each independently represent a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC-. Or -CONR-, preferably a single bond, -O-, -CO-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-. R represents a hydrogen atom, an alkyl group or an aryl group. The alkyl group represented by R preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. The aryl group represented by R preferably has 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms. R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

In the formula (D-2), C ¹ and C ² each independently represent a single bond or a divalent linking group. The divalent linking group is preferably an alkyl group, an aryl group or an alkyl group, more preferably an alkyl group or an alkyl group. The carbon number of the alkylene group and the oxygen alkyl group is preferably from 1 to 30, more preferably from 1 to 10. The alkyl group and the oxygen alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 12.

In the formula (D-2), P ² represents a substituent. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a hydroxymethyl group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Further, the substituent represented by P ² may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P ² may be the same or different. In the case where P ² is a monovalent polymer chain having a repeating unit and k is 1, P ² preferably has 2 to 20 (preferably 2 to 15 and further preferably 2 to 10) a monovalent polymer chain derived from a repeating unit of a vinyl compound. Further, when P ² is a monovalent polymer chain having a repeating unit and k is 2 or more, the average value of the number of repeating units derived from the vinyl compound of k P ² is preferably 2 to 20 One (preferably 2 to 15 and further preferably 2 to 10).

In the case where P ² represents a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P ² include other repeating units described in the dye multimer (A). The other repeating unit preferably has one or more selected from the group consisting of the repeating unit having an acid group and the repeating unit having a curable group. In the case where P ² comprises a repeating unit containing an acid group, the proportion of the repeating unit containing an acid group is preferably from 10 mol% to 80 mol%, more preferably 10 mol%, relative to all repeating units of P ² . %~65% by mole. In the case where P ² contains a repeating unit having a hardening group, the proportion of the repeating unit having a hardening group is preferably from 10 mol% to 80 mol%, more preferably 10, with respect to all repeating units of P ² . Mole% ~ 65 mol%.

In the formula (D-2), D ² represents a dye structure. The dye structure represented by D ² may be a polymer chain in which a part of the dye compound is bonded to -S- or a repeating unit having a dye structure in the main chain or the side chain. The polymer chain is not particularly limited as long as it contains a dye structure, and is preferably one selected from the group consisting of a (meth)acrylic resin, a styrene resin, and a (meth)acrylic acid/styrene resin. The repeating unit of the polymer chain is not particularly limited, and examples thereof include a repeating unit represented by the formula (A), a repeating unit represented by the formula (C), and the like. Further, the total of the repeating units having a dye structure among all the repeating units constituting the polymer chain is preferably from 5 mol% to 60 mol%, more preferably from 10 mol% to 50 mol%, and still more preferably 20 Mole% to 40% by mole. The polymer chain includes, in addition to the repeating unit having a dye structure, other repeating units described in the dye multimer (A). It is preferred to have one or more selected from the group consisting of a repeating unit having an acid group and a repeating unit having a curable group as another repeating unit.

Specific examples of the formula (D) include the followings. [化34] [化35] [化36]

The weight average molecular weight (Mw) of the dye multimer is preferably from 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and further preferably 6,000 or more. The upper limit is preferably 30,000 or less, and further preferably 20,000 or less. By satisfying the above range, it is easy to produce a cured film in which color unevenness and defects are suppressed. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye multimer [(Mw) / (Mn)] is preferably from 1.0 to 2.0, more preferably from 1.1 to 1.8, particularly preferably from 1.1 to 1.5. Further, in the present invention, the weight average molecular weight (Mw) of the dye multimer is a polystyrene-converted value measured by gel permeation chromatography (GPC), and specifically, by the following examples. The value measured by the method described.

The acid value of the dye multimer is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, further preferably 27 mgKOH/g or more, and particularly preferably 30 mgKOH/g or more. Further, the upper limit of the acid value is preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less, further preferably 180 mgKOH/g or less, particularly preferably 130 mgKOH/g or less, and further preferably 120 mgKOH/g. the following. By satisfying the above range, the developability is further improved, so that the development residue can be further reduced.

The curable base value of the dye multimer is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and still more preferably 0.3 mmol/g or more. When the curable base value is 0.1 mmol/g or more, a cured film excellent in light resistance or solvent resistance can be easily obtained. In addition, fading of the film caused by the developer, the stripper, or the like can be more effectively suppressed. The upper limit of the curable base value is not particularly limited, and is, for example, preferably 2.0 mmol/g or less, more preferably 1.5 mmol/g or less. The curable base value can be calculated by dividing the number of curable groups introduced into the dye multimer by the molecular weight of the dye multimer. Further, it can be actually measured by an analysis means such as ¹ H-NMR (nuclear magnetic resonance).

The colored composition of the present invention preferably contains 0.01% by mass to 50% by mass of the dye multimer in the total solid content of the colored composition of the present invention. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less. In the case where the colored composition of the present invention contains two or more kinds of dye multimers, the total amount thereof is preferably within the above range.

<<Other Coloring Agent>> The coloring composition of the present invention may further use a coloring agent (other coloring agent) other than the coloring matter polymer. The colored composition of the present invention preferably comprises other colorants. Other colorants may be either dye or pigment, or both. Other colorants are preferably pigments. In addition, other colorants may be pigment multimers.

As the pigment, various conventional inorganic pigments or organic pigments can be cited. The primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast. Further, from the viewpoint of dispersion stability, it is preferably 5 nm or more. The primary particle size of the pigment is preferably from 5 nm to 75 nm, more preferably from 5 nm to 55 nm, and particularly preferably from 5 nm to 35 nm. The primary particle size of the pigment can be measured by a known method such as an electron microscope.

Examples of the inorganic pigment include metal compounds such as a metal oxide and a metal salt, and specific examples thereof include black pigments such as carbon black and titanium black, and iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, and chromium. a metal oxide such as zinc or bismuth, and a composite oxide of the metal.

The following are mentioned as an organic pigment. However, the invention is not limited to these. Pigment Index (CI) Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 11 , CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31 , CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35:1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment 199, CI Pigment Yellow 213, CI Pigment Yellow 214, etc., CI Pigment Orange 2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17: 1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, etc., CI Pigment Red 1, Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53:1 CI Pigment Red 57:1, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81:1, CI Pigment Red 81:2, CI Pigment Red 81: 3, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255 , CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279, CI Pigment Green 7, Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 42, CI Pigment Blue (Pigment Blue) 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, CI Pigment Blue 80, and Pig Pigment Black 1. Further, as the green pigment, a zinc halide phthalocyanine pigment having an average of 10 to 14 halogen atoms in the molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms can be used. Specific examples thereof include the compounds described in WO2015/118720. In addition, as the yellow pigment, the quinophthalone pigments described in paragraphs 0011 to 0034 of JP-A-2013-54339, and paragraphs 0013 to 0558 of JP-A-2014-26228 may be used. Quinone pigments, etc. These organic pigments may be used singly or in combination of various organic pigments for the purpose of improving color purity.

For example, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent No. 2,592, 207, U.S. Patent No. 4,808, 501, U.S. Patent No. 5, 568, 850, U.S. Patent No. 5, 567, 950, U.S. Patent No. 5, 505, 950, Japanese Patent Laid-Open No. Hei 5- 333 207, Japanese Patent Laid-Open No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115 The dye disclosed in Japanese Laid-Open Patent Publication No. Hei 6-194928, and the like. If it is distinguished by a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triphenylmethane compound, an anthracene compound, a benzylidene compound, an oxophthalocyanine compound, or the like can be used. A pyrazolotriazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, or the like. Further, as the dye, a dye multimer can also be used.

Examples of the dye multimers include those disclosed in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, and the like. The compound described.

When the coloring composition of the present invention contains another coloring agent, the content of the other coloring agent is preferably from 10% by mass to 70% by mass based on the total solid content of the coloring composition. The upper limit is more preferably 60% by mass or less, and further preferably 50% by mass or less. The lower limit is more preferably 20% by mass or more, and still more preferably 25% by mass or more. Further, the colored composition of the present invention may be in a form that does not substantially contain other coloring agents. In addition, it is preferable that the coloring agent does not contain other coloring agents, for example, the total amount of the coloring agent (the total mass of the dye multimer of the present invention and other coloring agents) is preferably 0.1% by mass or less, more preferably 0.05% by mass. Below %, it is especially preferred that no other colorants are included.

<<Resin>> The coloring composition of the present invention preferably contains a resin. The resin is blended, for example, in a use for dispersing a pigment or the like in a composition or a use of a binder. Further, a resin mainly used for dispersing a colorant such as a pigment is also referred to as a dispersant. Among them, such a use of the resin is an example, and it can also be used for purposes other than such use.

In the colored composition of the present invention, the content of the resin is preferably from 10% by mass to 80% by mass based on the total solid content of the coloring composition. The lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

<<<Dispersant>>> The coloring composition of the present invention preferably contains a dispersant in the form of a resin. The dispersing agent preferably contains at least an acidic dispersing agent, more preferably an acidic dispersing agent. When the dispersant contains at least an acidic dispersant, the dispersibility of the pigment is improved, and it is difficult to cause unevenness in brightness. Further, since excellent developability can be obtained, pattern formation can be preferably performed by photolithography. Further, the dispersant is only an acidic dispersant. For example, the content of the acidic dispersant in the total mass of the dispersant is preferably 99% by mass or more, and may be 99.9% by mass or more.

Here, the acidic dispersant (acid resin) means a resin in which the amount of the acid group is larger than the amount of the basic group. When the total amount of the acid group and the amount of the basic group is 100 mol%, the acidic dispersant (acid resin) is preferably a resin having an acid group content of 70 mol% or more, more preferably substantially A resin containing only an acid group. The acid group of the acidic dispersant (acid resin) is preferably a carboxyl group. Further, the basic dispersant (basic resin) means a resin in which the amount of the basic group is more than the amount of the acid group. When the total amount of the acid group and the amount of the basic group is 100 mol%, the alkaline dispersant (basic resin) is preferably a resin having a basic group content of 50 mol% or more. The basic group possessed by the alkaline dispersant is preferably an amine. The acid value of the acidic dispersant (acid resin) is preferably from 40 mgKOH/g to 105 mgKOH/g, more preferably from 50 mgKOH/g to 105 mgKOH/g, and still more preferably from 60 mgKOH/g to 105 mgKOH/g.

Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified Poly (meth) acrylate, (meth) acryl copolymer, naphthalene sulfonate condensate], polyoxyalkylene alkyl phosphate, polyoxyethylamine, alkanolamine, etc. .

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure. The polymer dispersant functions to adsorb on the surface of the pigment to prevent re-agglomeration. Therefore, a terminal modified polymer having a blocking portion on the surface of the pigment, a graft polymer, and a block polymer are preferable.

As the resin (dispersant), a graft copolymer containing a repeating unit represented by any one of the following formulas (1) to (4) can also be used.

[化37]

In the formulae (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently Represents a hydrogen atom or a monovalent organic group, and Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a monovalent organic group, and n, m, p, and q each independently represent an integer of 1 to 500, and j and k each independently represent an integer of 2 to 8, In the formula (3), when p is from 2 to 500, a plurality of R ³ may be the same or different, and in the formula (4), when q is from 2 to 500, a plurality of X ⁵ and R ^{4 are present.} They may be the same or different from each other.

W ¹ , W ² , W ³ , and W ^{4 are} preferably oxygen atoms. X ¹ , X ² , X ³ , X ⁴ and X ^{5 are} preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, and particularly preferably a methyl group. Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the connection is not particularly limited depending on the structure. The structure of the monovalent organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ is not particularly limited, and specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group. An alkyl sulfide group, an aryl sulfide group, a heteroaryl sulfide group, an amine group, and the like. Among these, the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ are preferably groups having a steric repulsion effect, and are preferably independently independent from the viewpoint of improving dispersibility. The ground is an alkyl group or alkoxy group having 5 to 24 carbon atoms, and particularly preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or a carbon number of 5 to 5 carbon atoms. 24 alkoxy groups. Further, the alkyl group contained in the alkoxy group may be any of a linear chain, a branched chain, and a cyclic group.

In the formulae (1) to (4), n, m, p, and q are each independently an integer of from 1 to 500. Further, in the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoints of dispersion stability and developability, j and k in the formulae (1) and (2) are preferably an integer of 4 to 6, and most preferably 5.

In the formula (3), R ³ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different from each other.

In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group. The monovalent organic structure is not particularly limited based on the structure. R ^{4 is} preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is more preferable. The linear alkyl group having 1 to 20 carbon atoms is particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In the formula (4), when q is from 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different.

Regarding the graft copolymer, the description of Paragraph No. 0025 to Paragraph No. 0094 of JP-A-2012-255128 is incorporated herein by reference. Specific examples of the graft copolymer include, for example, the resin described in Paragraph No. 0072 to Paragraph No. 0094 of JP-A-2012-255128, which is incorporated herein by reference.

Further, the resin (dispersant) may be used in an oligomeric oligoimine-based dispersant containing at least one of a main chain and a side chain. The oligomer-imine-based dispersant is preferably a resin having a repeating unit and a side chain and having a basic nitrogen atom in at least one of the main chain and the side chain, and the repeating unit contains a functional group having a pKa of 14 or less. A partial structure X, the side chain comprising a side chain Y having an atomic number of 40 to 10,000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

For the oligo-imine-based dispersing agent, the description of Paragraph No. 0102 to Paragraph No. 0174 of JP-A-2012-255128 is incorporated herein by reference. As a specific example of the oligomeric imide-based dispersing agent, for example, the resin described in Paragraph No. 0168 to Paragraph No. 0174 of JP-A-2012-255128 can be used.

The dispersing agent can also be obtained as a commercial product, and as such a specific example, "DA-7301" manufactured by Nanben Chemical Co., Ltd.; "Disperbyk" manufactured by BYK Chemie Co., Ltd. (Disperbyk) -101 (polyamidoamine phosphate), 107 (carboxylate), 110 (copolymer containing acid group), 111 (phosphate dispersant), 130 (polyamine), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid); Evka (EFKA) manufactured by EFKA 4047, 4050 ~ 4165 (polyurethane type), Efka (EFKA) 4330 ~ Evka (EFKA) 4340 (block copolymer), 4400 ~ 4402 (modified polyacrylate), 5010 ( Polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)"; Ajinomoto Fine-Chemistry "Ajisper PB821, PB822, PB880, PB881" manufactured by Techno); "Flowlen TG-710 (urethane oligomer), Polyflow No. 50E, No. 300 (acrylic copolymer)" manufactured by Nippon Chemical Co., Ltd. "Disparlon" KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; Demol RN, N (formalin polycondensate), MS, C, SN-B (aromatic polycondensate), Homogenol L manufactured by Kao Corporation -18 (polymer polycarboxylic acid), Emulgen 920, 930, 935, 985 (polyoxyethylidene phenyl ether), acetaxel (Acetamin) 86 (stearylamine) Acetate)": Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) manufactured by Lubrizol, Japan , 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (grafted polymers); Nikko (Nikko) "Nikkol T106 (polyoxyethyl sorbitan monooleate), MYS-IEX (polyoxyethylidene monostearate)" manufactured by Chemicals); "Hinoact T-8000E" manufactured by Kawaken Fine Chemicals Co., Ltd.; "organic siloxane polymer KP341" manufactured by Shin-Etsu Chemical Co., Ltd.; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Evka EFKA) Polymer 401, Efka (EFKA) Polymer 450"; Disperse Aid 6, Dispas Ed (made by San Nopco) Disperse Aid) 8, Disperse Aid 15, Disperse Aid 9100, and other polymer dispersants; Eddie Science, made by ADEKA Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108 L121, P-123 "; and" Iao Knight (Ionet) (trade name) S-20 ", etc. Sanyo Chemical (shares) manufacture. In addition, Acrybase FFS-6752, Acrybase FFS-187, Acrycure RD-F8, and Cyclomer P can also be used. Further, the resin described as the dispersant can also be used for applications other than the dispersant. For example, it can also be used as a binder.

<<<Alkali Soluble Resin>>> The coloring composition of the present invention may contain an alkali-soluble resin as a resin. The developability and pattern formability are improved by containing an alkali-soluble resin. Further, an alkali-soluble resin can also be used as a dispersing agent or a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably from 5,000 to 100,000. Further, the number average molecular weight (Mn) is preferably from 1,000 to 20,000. The alkali-soluble resin can be suitably selected from the following alkali-soluble resins, and the alkali-soluble resin can be a linear organic polymer, and is preferably a molecule (preferably an acrylic copolymer or a styrene copolymer). The molecule of the chain has at least one group that promotes alkali solubility.

The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of controlling developability, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable. Examples of the base which promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are preferably soluble in an organic solvent and may be weakly alkaline. As the developer of the aqueous solution, (meth)acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.

For the production of an alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and can also be experimentally conducted. Determine the conditions sexually.

The alkali-soluble resin is preferably a polymer having a carboxyl group in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer, and a partial esterification. An alkali-soluble phenol resin such as a maleic acid copolymer or a novolac type resin, and an acid anhydride derivative having a carboxyl group in a side chain, and an acid anhydride added to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is preferred as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc., as the vinyl compound, styrene, α-methylstyrene, vinyl toluene , glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. . In addition, as the other monomer, the N-substituted maleimide monomer described in Japanese Patent Laid-Open Publication No. Hei 10-300922 can be used. For example, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are mentioned. Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

As the alkali-soluble resin, a benzyl (meth)acrylate/(meth)acrylic acid copolymer, a benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer can be preferably used. A multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, 2-hydroxypropyl (meth)acrylate/polystyrene described in JP-A-7-140654, which is a copolymer of 2-hydroxyethyl (meth)acrylate, can also be preferably used. Macromonomer/Benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/A Benzyl acrylate / methacrylic acid copolymer and the like. In addition, as a commercial item, for example, FF-426 (made by Fujikura Kasei Co., Ltd.) or the like can be used.

Further, as the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can also be used. Examples of the polymerizable group include a (meth)allyl group and a (meth)acrylonitrile group. Among the alkali-soluble resins having a polymerizable group, an alkali-soluble resin having a polymerizable group in a side chain or the like is useful. Examples of the alkali-soluble resin having a polymerizable group include: Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), and Photomer 6173 (polyurethane-based oligosaccharide containing COOH). Polymer, manufactured by Diamond Shamrock Co., Ltd., Biscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Sekuroma ( Cyclomer) P series (for example, ACA230AA), Placcel CF200 series (all manufactured by Daicel), Ebecryl 3800 (made by UCB Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

The alkali-soluble resin is also preferably a polymer comprising a compound represented by the following formula (ED1) and/or a formula (1) of JP-A-2010-168539. The monomer components of the compound (hereinafter, some of these compounds are also referred to as "ether dimers") are polymerized.

[化38]

In the formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

As a specific example of the ether dimer, for example, reference is made to paragraph 0317 of Japanese Patent Laid-Open Publication No. 2013-29760, which is incorporated herein by reference. The ether dimer may be used alone or in combination of two or more.

The alkali-soluble resin may also contain a repeating unit derived from a compound represented by the following formula (X). [39] In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may include a benzene ring. n represents an integer of 1 to 15.

In the formula (X), the alkyl group of R ₂ preferably has 2 to 3 carbon atoms. Further, the alkyl group of R ₃ has a carbon number of from 1 to 20, more preferably from 1 to 10, and the alkyl group of R ₃ may contain a benzene ring. As the alkyl group R contains a benzene ring represented by ₃ include benzyl, 2-phenyl (iso) propyl and the like.

Specific examples of the alkali-soluble resin include the following resins. In the following formula, Me is a methyl group. [化40]

The alkali-soluble resin can be referred to the descriptions of paragraphs 0558 to 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the specification of [0685] to [0700]). Enter this manual. Further, the copolymer (B) described in Paragraph No. 0029 to Paragraph 0063 of JP-A-2012-32767, and the alkali-soluble resin used in the examples, and JP-A-2012-208474 can be used. The adhesive resin described in the paragraphs 0088 to 0098 and the adhesive resin used in the examples, and the adhesive resin described in paragraph number 0022 to paragraph 0032 of JP-A-2012-137531 The adhesive resin used in the example, the adhesive resin described in Paragraph No. 0132 to Paragraph No. 0143 of JP-A-2013-024934, and the adhesive resin used in the Example, Japanese Patent Laid-Open No. 2011-242752 The adhesive resin described in Paragraph No. 0092 to Paragraph No. 0098 of the Japanese Patent Laid-Open No. 0098 and the Examples, and the adhesive resin described in Paragraph No. 0030 to Paragraph No. 0072 of JP-A-2012-032770. This content is incorporated into this specification.

The acid value of the alkali-soluble resin is preferably from 30 mgKOH/g to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and further preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, further preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less.

The content of the alkali-soluble resin is preferably from 0.1% by mass to 20% by mass based on the total solid content of the colored composition. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The colored composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds. When two or more types are contained, it is preferable that the total amount is the said range.

<<Solvent>> The coloring composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the coloring composition.

Examples of the organic solvent include the following. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxylate, butyl alkoxy acetate (for example) , methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (For example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxyl) Methyl propyl propionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (Example: methyl 2-alkoxypropionate, 2-alkoxypropionic acid) Ethyl ester, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxyl Methyl propyl propionate, ethyl 2-ethoxypropionate), 2-alkoxy-2-methylpropanoate and Ethyl 2-alkoxy-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.), acetone Methyl ester, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc.; and as ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; Further, examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone; and, as the aromatic hydrocarbon, for example, preferably exemplified : Toluene, xylene, and the like.

The organic solvent may be used alone or in combination of two or more. In the case where two or more organic solvents are used in combination, it is particularly preferred to include a methyl ester selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol A mixed solution of two or more of acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

In the present invention, the content of the peroxide of the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially no peroxide.

The content of the solvent is preferably such an amount that the total solid content of the colored composition is from 5% by mass to 80% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

<<Curable Compound>> The colored composition of the present invention contains a curable compound. As the curable compound, a known compound which can be crosslinked by a radical, an acid or heat can be used. For example, a compound containing a group having an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane) group, or a methylol group can be mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. In the present invention, the curable compound is preferably a polymerizable compound, more preferably a radical polymerizable compound.

The content of the curable compound is preferably from 0.1% by mass to 50% by mass based on the total solid content of the colored composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and still more preferably 40% by mass or less. The curable compound may be used alone or in combination of two or more. In the case where two or more types are used in combination, it is preferred that the total amount is within the above range.

(Polymerizable compound) In the present invention, the polymerizable compound may be, for example, a monomer, a prepolymer, that is, a dimer, a trimer, or an oligomer, or a mixture thereof, and a chemical form such as a polymer. Any of them. When the polymerizable compound is a photoradical polymerizable compound, it is preferably a monomer. The molecular weight of the polymerizable compound is preferably from 100 to 3,000. The upper limit is preferably 2,000 or less, and more preferably 1,500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. The polymerizable compound is preferably a trifunctional to pentafunctional (meth) acrylate compound, more preferably a trifunctional to hexafunctional (meth) acrylate compound. As a specific compound, the paragraph number 0095 to the paragraph number 0108 of the Japanese Patent Laid-Open Publication No. 2009-288705, the paragraph 0227 of the Japanese Patent Laid-Open Publication No. 2013-29760, and the Japanese Patent Laid-Open No. 2008-292970 The compound described in Paragraph No. 0254 to Paragraph No. 0257 is incorporated in the present specification.

The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as Kayad) (KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.; A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and A structure in which a methyl group acrylonitrile group is bonded via an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499 commercially available from Sartomer Co., Ltd.). These types of oligomers can also be used. In addition, KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. In addition, the following compounds can also be used. [化41]

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. For example, M-305, M-510, M-520, etc. which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. are mentioned as a commercial item.

The preferred acid value of the polymerizable compound having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production or handling. Further, the photopolymerization performance is good and the curability is excellent.

Among the polymerizable compounds, a compound having a caprolactone structure is also preferred. The polymerizable compound having a caprolactone structure is commercially available, for example, from the KAYARAD DPCA series from Japan Chemicals Co., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like. .

As the polymerizable compound, a polymerizable compound having an alkoxy group can also be used. The polymerizable compound having an alkoxy group is preferably a polymerizable compound having an ethoxy group and/or a propoxy group, and further preferably a polymerizable compound having an ethoxy group, more preferably 4 to 20 An ethoxylated trifunctional to hexafunctional (meth) acrylate compound.

Specific examples of the polymerizable compound having an alkoxy group include the following compounds. [化42]

As a commercial item of the polymerizable compound having an alkoxy group, for example, SR-494, which is a tetrafunctional acrylate having four ethylene oxide groups, manufactured by Sartomer Co., Ltd., is known as Nippon Chemical Co., Ltd. A hexafunctional acrylate having six pentyloxy groups, that is, DPCA-60, a trifunctional acrylate having three isobutoxy groups, that is, TPA-330, or the like, was produced.

The polymerizable compound is as described in JP-A-48-41708, JP-A-53-37193, JP-A-2-332293, and JP-A-2-16765. Amino acrylate acrylates, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, Japanese Patent Publication No. SHO 62-39418 The urethane compound having an ethylene oxide skeleton described above is also preferred. In addition, it is preferable to use an amine group structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. An addition polymerizable compound of a thioether structure. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and DPHA-40H (Nippon Chemical Co., Ltd.) Manufactured by the company), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

When a polymerizable compound is used as the curable compound, the content of the polymerizable compound is preferably from 0.1% by mass to 50% by mass based on the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and still more preferably 40% by mass or less. The curable compound may be used alone or in combination of two or more. In the case where two or more types are used in combination, it is preferred that the total amount is within the above range. Further, the content of the polymerizable compound is preferably from 10% by mass to 100% by mass, and more preferably from 30% by mass to 100% by mass based on the total mass of the curable compound.

(Compound having an epoxy group) In the present invention, a compound having an epoxy group can also be used as the curable compound. The compound having an epoxy group is preferably a compound having two or more epoxy groups in one molecule. The epoxy group preferably has 2 to 100 in one molecule. The upper limit may be, for example, 10 or less, or may be 5 or less.

The compound having an epoxy group in the present invention preferably has a structure having an aromatic ring and/or an aliphatic ring, and further preferably has an aliphatic ring structure. The epoxy group is preferably bonded to the aromatic ring and/or the aliphatic ring via a single bond or a linking group. The linking group may, for example, be an alkyl group selected from an alkyl group, an extended aryl group, -O-, or -NR'- (R' represents a hydrogen atom, may have a substituent, or may have a substituent, preferably A structure represented by a hydrogen atom), a group of at least one of -SO ₂ -, -CO-, -O-, and -S-. In the case of a compound having an aliphatic ring, a compound in which an epoxy group is directly bonded (single bond) to an aliphatic ring is preferred. In the case of a compound having an aromatic ring, a compound in which an epoxy group is bonded to an aromatic ring via a linking group is preferred. The linking group is preferably a group containing an alkyl group or a combination of an alkyl group and -O-. Further, as the compound having an epoxy group, a compound having a structure in which two or more aromatic rings are bonded by a hydrocarbon group can also be used. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. The epoxy group is preferably linked via the linking group.

The epoxy equivalent of the compound having an epoxy group (= the molecular weight of the compound having an epoxy group / the number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 g/eq to 400 g/eq. Further preferably, it is from 100 g/eq to 300 g/eq.

The compound having an epoxy group may be a low molecular compound (for example, a molecular weight of less than 2,000, and a molecular weight of less than 1,000), or may be a macromolecule (for example, a molecular weight of 1,000 or more, in the case of a polymer, a weight average) Any one of molecular weights of 1,000 or more. The weight average molecular weight of the epoxy group-containing compound is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the weight average molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,500 or less.

For the compound having an epoxy group, paragraph number 0034 to paragraph number 0036 of JP-A-2013-011869, paragraph number 0147 to paragraph number 0156 of Japanese Patent Laid-Open No. 2014-043556, and Japanese Patent Laid-Open Publication No. 2014 The compound described in Paragraph No. 0085 to Paragraph No. 0092 of Japanese Patent Publication No. 089408. This content is incorporated into this specification. As a commercial product, for example, bisphenol A type epoxy resin is jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above is manufactured by Mitsubishi Chemical Co., Ltd.), Abby clone ( EPICLON) 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by Di Aisheng (DIC) Co., Ltd.), bisphenol F epoxy resin jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above is manufactured by Mitsubishi Chemical Co., Ltd.), Epiclon 830, EPICLON 835 (above produced by Di Aisheng (DIC) Co., Ltd.) , LCE-21, RE-602S (the above is manufactured by Nippon Chemical Co., Ltd.), etc., phenol novolac type epoxy resin is jER152, jER154, jER157S70, jER157S65 (above is manufactured by Mitsubishi Chemical Co., Ltd.), Abby clone (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N-775 (above, manufactured by Di Aisheng (DIC) Co., Ltd.), etc., cresol novolac type epoxy resin Abby Clone (EPICL) ON) N-660, Epiclon N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, Abby clone EPICLON) N-690, EPICLON N-695 (above is manufactured by Di Ai Sheng (DIC) Co., Ltd.), EOCN-1020 (above is manufactured by Nippon Chemical Co., Ltd.), aliphatic epoxy resin ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA) , Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, Aibo EPOLEAD PB 4700 (above made by Daicel), Denacol EX-212L, Denacol EX-214L, Denacol EX -216L, Denacol EX-321L, Denacol EX-850L (above is Nagase Chemte) X) (share) manufacturing) and so on. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN can also be cited. ) EP-4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above ADEKA) ) (manufacturing), jER1031S (Mitsubishi Chemical Co., Ltd.), etc.

When a compound having an epoxy group is used as the curable compound, the content of the compound having an epoxy group is preferably from 0.1% by mass to 40% by mass based on the total solid content of the coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more. In the case where two or more types are used in combination, it is preferred that the total amount is within the above range. Further, the content of the epoxy group-containing compound is preferably from 1% by mass to 80% by mass, and more preferably from 1% by mass to 50% by mass based on the total mass of the curable compound. Further, in the case where a polymerizable compound and a compound having an epoxy group are used in combination, the mass of the polymerizable compound and the compound having an epoxy group is preferably a polymerizable compound: a compound having an epoxy group = 100:1 to 100: 400, more preferably 100:1 to 100:100.

<<Curing accelerator>> The coloring composition of the present invention may be added with a curing accelerator for the purpose of promoting the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The polyfunctional thiol compound can also be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following formula (T1). General formula (T1) [化43] (In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group)

In the above formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2, and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and particularly preferred are compounds represented by the formula (T2). These polyfunctional thiol compounds may be used alone or in combination of two or more.

[化44]

Further, as the hardening accelerator, a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963), an amine, a phosphonium salt, a phosphonium salt, or a guanamine compound can also be used. (The above-mentioned, for example, the curing agent described in paragraph 0186 of JP-A-2013-41165), an alkali generating agent (for example, an ionic compound described in JP-A-2014-55114), and a cyanate compound ( For example, the compound described in paragraph 0071 of JP-A-2012-150180, an alkoxydecane compound (for example, an alkoxydecane compound having an epoxy group described in JP-A-2011-253054), The onium salt compound (for example, a compound exemplified as an acid generator in paragraph 0216 of JP-A-2015-34963, a compound described in JP-A-2009-180949), and the like.

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably from 0.3% by mass to 8.9% by mass, and more preferably from 0.8% by mass to 6.4% by mass based on the total solid content of the coloring composition. %.

<<Photopolymerization Initiator>> The coloring composition of the present invention preferably further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the light in the ultraviolet region to the visible region is photosensitive. Further, it may be an active agent which generates a living radical by a certain action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization in accordance with the kind of the monomer. Further, the photopolymerization initiator is preferably a compound having at least one molecular absorption coefficient of at least about 50 in the range of from about 300 nm to 800 nm, more preferably from 330 nm to 500 nm.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone. A commercially available product of a trihalomethyltriazine-based photopolymerization initiator is TAZ-107 (manufactured by Green Chemical Co., Ltd.).

Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, and a mercaptophosphine compound. , phosphine oxide compound, metallocene compound, hydrazine compound, triarylimidazole compound, benzimidazole compound, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene- A compound of the group consisting of a benzene-iron complex and a salt thereof, a halogenated methyl oxadiazole compound, and a 3-aryl-substituted coumarin compound. The following compounds are mentioned as a triaryl imidazole compound, a benzimidazole compound, and a benzophenone compound. [化45]

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used. As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjia can be used. IRGACURE-127 (trade name, manufactured by BASF). As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names, both of which are commercially available) can be used. Made for BASF). As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which has an absorption wavelength matching a long-wavelength source such as 365 nm or 405 nm, can also be used. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name, all manufactured by BASF) can be used as a commercial product.

In particular, when the coloring composition of the present invention is used for the production of a color filter of a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. Therefore, it is important that the hardenability and the unexposed portion are not present. The residue was developed. From this point of view, it is particularly preferred to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, the exposure for curing is a stepper, but the exposure machine is damaged by halogen, and the amount of photopolymerization initiator must be suppressed. In view of these aspects, it is particularly preferable to use a ruthenium compound when forming a fine pattern like a solid-state image sensor. In addition, color mobility can be further improved by using a ruthenium compound. As a specific example of the photopolymerization initiator, for example, reference is made to paragraph 0265 to paragraph 0268 of JP-A-2013-29760, which is incorporated herein by reference.

As a photopolymerization initiator, a ruthenium compound is more preferable. As a specific example of the oxime initiator, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used.

As the hydrazine compound such as an anthracene derivative which can be preferably used as a photopolymerization initiator in the present invention, for example, 3-benzylideneoxyimidobutan-2-one, 3-ethyloxene Isoaminobutan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxy Amino-1-phenylpropan-1-one, 2-benzylideneoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane 2-ketone, 2-ethoxycarbonyloxyimido-1-phenylpropan-1-one, and the like.

As the ruthenium compound, "JCS Perkin II" (June 1753-1660), "The British Chemical Society - Purkin II" (JCS Perkin II) ("(1979) pp. 156-162), "Journal of Photopolymer Science and Technology" ((1995) pp. 202-232), Japanese Patent Laid-Open 2000-66385 The compound described in each of the publications of Japanese Laid-Open Patent Publication No. JP-A-2006-342166, and JP-A-2006-342166. In the commercial product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be preferably used. In addition, you can also use TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.) , LTD)), Adeka Arkls NCI-930 (made by ADEKA).

In addition, as the ruthenium compound other than the above, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is bonded to the N-position of the carbazole ring, and a hetero substituent introduced to the benzophenone moiety may be used. The compound described in the Japanese Patent Publication No. 7626957, the compound described in Japanese Patent Laid-Open Publication No. 2010-15025, and the Japanese Patent Publication No. 2009-292039, the disclosure of which is incorporated herein by reference. The ketone oxime compound described in Japanese Patent No. 7556910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm and a good sensitivity to a g-ray source. A compound or the like described in JP-A-2009-221114. For example, it is preferable to refer to paragraph 0274 to paragraph 0275 of Japanese Patent Laid-Open Publication No. Hei. No. 2013-29760, the entire contents of which is incorporated herein. Specifically, the quinone compound is preferably a compound represented by the following formula (OX-1). Further, it may be a ruthenium compound in which the N-O bond of ruthenium is (E), or may be a ruthenium compound of the (Z) form, or may be a mixture of the (E) form and the (Z) form.

[Chem. 46]

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. In addition, the groups may have one or more substituents. Further, the substituent may be further substituted with another substituent. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group. In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. The groups may also have more than one substituent. The substituent may be exemplified as the substituent. In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group or an alkynylene group having 1 to 12 carbon atoms. The groups may also have more than one substituent. The substituent may be exemplified as the substituent.

The ruthenium compound having an anthracene ring can also be used as a photopolymerization initiator in the present invention. Specific examples of the ruthenium compound having an anthracene ring include the compounds described in JP-A-2014-137466. This content is incorporated into the present specification.

The present invention can also use a ruthenium compound having a fluorine atom as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include a compound described in JP-A-2010-262028, a compound 24 described in JP-A-2014-500852, a compound 36 to a compound 40, and a Japanese patent. Compound (C-3) or the like described in Japanese Patent Publication No. 2013-164471. This content is incorporated into the present specification.

The present invention can use a ruthenium compound having a nitro group as a photopolymerization initiator. Specific examples of the ruthenium compound having a nitro group include paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 of JP-A-2014-137466, and paragraphs 0070 to 0079. The compound described in the above, or Adeka Arkls NCI-831 (manufactured by ADEKA).

Specific examples of the ruthenium compound which can be preferably used in the present invention are shown below, but the present invention is not limited thereto.

[化47] [48]

The ruthenium compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in a wavelength range of 360 nm to 480 nm, particularly preferably having a high absorbance at 365 nm and 405 nm. compound of.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000. A known method can be used for the measurement of the molar absorption coefficient of the compound. Specifically, for example, a Kerry-5 spectrophotometer (Vary-5 spectrophotometer manufactured by Varian) is preferably used by an ultraviolet-visible spectrophotometer. )) and using an ethyl acetate solvent and measuring at a concentration of 0.01 g/L. The photopolymerization initiator may also be used in combination of two or more kinds as needed.

In the case where the coloring composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1% by mass to 50% by mass, more preferably 0.5% by mass based on the total solid content of the coloring composition. % to 30% by mass, and more preferably 1% by mass to 20% by mass. More good sensitivity and pattern formation can be obtained within this range. The coloring composition of the present invention may contain only one photopolymerization initiator, and may contain two or more kinds. When two or more types are contained, it is preferable that the total amount is the said range.

<<Pigment Derivative>> The coloring composition of the present invention may contain a pigment derivative. The pigment derivative may be a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or a phthalimine methyl group. Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. , a purple ring ketone pigment, an anthraquinone pigment, a thioindigo pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, an indanthrene pigment, a metal Compound pigments and the like. Further, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium salt group thereof are preferable, and a carboxylic acid group and a sulfonic acid group are preferable, and a sulfonic acid group is particularly preferable. The basic group which the pigment derivative has is preferably an amine group, and particularly preferably a tertiary amine group. As a specific example of the pigment derivative, the description of paragraphs 0162 to 0183 of JP-A-2011-252065 is incorporated herein by reference.

The content of the pigment derivative in the colored composition of the present invention is preferably from 1% by mass to 30% by mass, and more preferably from 3% by mass to 20% by mass based on the total mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

<<Interfacial Active Agent>> The colored composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

By containing a fluorine-based surfactant in the colored composition of the present invention, the solution characteristics (especially fluidity) when the coating liquid is prepared are further improved, and the uniformity of the coating thickness or the liquid-saving property can be further improved. In other words, when a film is formed using a coating liquid to which a coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered to wett the surface to be coated. It is improved and the coatability to the coated surface is improved. Therefore, film formation of a uniform thickness having a small thickness unevenness can be more preferably performed.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing content ratio of the fluorine-based surfactant in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac. F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac RS-72-K (above produced by Di Aisheng (DIC)); Froude (Fluorad) FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (share)); Surfolon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, sand Surflon SC-383, Surflon S393, sand Long (Surflon) KH-40 (Asahi Glass (shares) manufactured); PF636, PF656, PF6320, PF6520, PF7002 (OMNOVA as above (OMNOVA) Co., Ltd.). As the fluorine-based surfactant, the compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. A block polymer can also be used as the fluorine-based surfactant. Specific examples thereof include a compound described in JP-A-2011-89090. As the fluorine-based surfactant, a repeating unit derived from a (meth) acrylate compound having a fluorine atom and an alkoxy group derived from two or more (preferably five or more) may be preferably used. A fluorine-containing polymer compound of a repeating unit of a (meth) acrylate compound (preferably an ethoxy group or a propoxy group), and the following compound can also be used as a fluorine-based surfactant used in the present invention. Illustrative. [化49] The weight average molecular weight of the compound is preferably from 3,000 to 50,000, for example, 14,000. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megafac RS-101 manufactured by DIC Corporation. RS-102, RS-718K, etc.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin C). Oxylate, glycerol ethoxylate, etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl alkenyl ether, polyoxyethylene ethyl octyl Phenyl ether, polyoxyethylene ethyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF) Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Solsperse 20000 ( Lubrizol (manufactured by Japan) and so on. In addition, Pionin D-6112-W, D-6315, etc., manufactured by Nippon Oil Co., Ltd., NCW-101, NCW-1001, NCW-1002, and Nippon Oil Co., Ltd. can also be used.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Industry ( (manufacturing)), (meth)acrylic (co)polymers Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yu Shang ( Share) manufacturing) and so on.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusei Co., Ltd.), Sanded BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

Examples of the anthrone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, and Toray Silicone. SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above Toray Dow) Corning), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above) It is manufactured by Shin-Etsu Chemical Co., Ltd.), BYK 307, BYK 323, BYK 330 (above, BYK Chemie).

The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass based on the total solid content of the coloring composition.

<<Chane coupling agent>> The coloring composition of the present invention may contain a decane coupling agent. The decane coupling agent is also preferably a decane compound having at least two functional groups having different reactivity in one molecule, and particularly preferably having an amine group and an alkoxy group as a functional group. As such a decane coupling agent, for example, N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), N-β -Aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-triethyl Oxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl - Triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503), etc. . For details of the decane coupling agent, the description of Paragraph No. 0155 to Paragraph No. 0158 of JP-A-2013-254047 is incorporated herein by reference.

When the coloring composition of the present invention contains a decane coupling agent, the content of the decane coupling agent is preferably 0.001% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass based on the total solid content of the coloring composition. % is particularly preferably from 0.1% by mass to 5% by mass. The colored composition of the present invention may contain only one decane coupling agent, and may contain two or more kinds. When two or more types are contained, it is preferable that the total amount is the said range.

<<Polymerization Inhibitor>> The coloring composition of the present invention preferably further contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, and benzoquinone. 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-Asia Nitrophenylhydroxylamine salt (ammonium salt, trivalent phosphonium salt, etc.) and the like. When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from 0.01% by mass to 5% by mass based on the total solid content of the coloring composition. The coloring composition of the present invention may contain only one polymerization inhibitor, and may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range.

<<Other Additives>> Various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anticoagulant, and the like can be formulated as needed in the coloring composition of the present invention. As such additives, the additives described in paragraphs 0155 to 0156 of JP-A-2004-295116 can be cited, and these contents are incorporated in the present specification. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0942 of JP-A-2011-90147), a thioether compound, or the like can be used. As a commercial item, for example, the ADEKASTAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO) manufactured by ADEKA Co., Ltd. can be cited. -60, AO-60G, AO-80, AO-330, etc.). Antioxidants may also be used in combination of two or more. The coloring composition of the present invention may contain the sensitizer or the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization prevention described in paragraph 0081 of JP-A-2004-295116. Agent.

In the coloring composition, the metal element is contained in the coloring composition, and the content of the second group element (calcium, magnesium, etc.) in the coloring composition is preferably 50. Below ppm, and preferably controlled to be from 0.01 ppm to 10 ppm. Further, the total amount of the inorganic metal salt in the colored composition is preferably 100 ppm or less, more preferably 0.5 ppm to 50 ppm.

<Method for Preparing Colored Composition> The colored composition of the present invention can be prepared by mixing the components. The order of input or the working conditions at the time of preparation are not particularly restricted. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions or dispersions, and these may be mixed at the time of application (at the time of coating). And prepared.

In the preparation of the colored composition, it is preferred to filter by a filter for the purpose of removing foreign matter or reducing defects. The filter is not particularly limited as long as it is a filter used for filtration purposes or the like from the past. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6 or nylon-6,6), or a polyolefin such as polyethylene or polypropylene (PP) may be used. A filter for raw materials such as a resin (including a high-density, ultra-high molecular weight polyolefin resin). Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred. The pore diameter of the filter is suitably from about 0.01 μm to about 7.0 μm, preferably from about 0.01 μm to about 3.0 μm, and more preferably from about 0.05 μm to about 0.5 μm. By setting it as this range, the fine foreign material, such as the formation of a uniform composition, or formation of a smooth film, can be removed reliably in the procedure mentioned later. In addition, it is preferable to use a fibrous filter material, and examples of the filter material include polypropylene fiber, nylon fiber, and glass fiber. Specifically, an SBP type series (SBP008, etc.) manufactured by Roki Techno Co., Ltd. can be used. ), TPR type series (TPR002, TPR005, etc.), SHPX series (SHPX003, etc.) filter cartridge.

Different filters can also be combined when using filters. In this case, the filtration by the first filter may be performed only once or twice or more. Further, the first filters having different pore diameters may be combined in the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Pall Co., Ltd. (DFA4201NXEY, etc.), Advantec Toyo Co., Ltd., and Nihon Entegris Co., Ltd. ( Selected from various filters provided by Japan's Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd. As the second filter, a filter formed of the same material or the like as the first filter can be used. For example, the filtration by the first filter may be performed only by the dispersion, or the other components may be mixed and then the second filtration may be performed.

<Pigment Multimer> Next, the dye multimer of the present invention will be described. The dye multimer of the present invention is a dye multimer having a dye structure represented by the above formula (I-1) or formula (I-2). The details of the formula (I-1) and the formula (I-2) are the same as those described in the colored composition.

The weight average molecular weight (Mw) of the dye multimer is preferably from 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and further preferably 6,000 or more. The upper limit is preferably 30,000 or less, and further preferably 20,000 or less. By satisfying the above range, it is easy to produce a cured film in which color unevenness and defects are suppressed. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye multimer [(Mw) / (Mn)] is preferably from 1.0 to 2.0, more preferably from 1.1 to 1.8, particularly preferably from 1.1 to 1.5. Further, in the present invention, the weight average molecular weight (Mw) of the dye multimer is a polystyrene-converted value measured by gel permeation chromatography (GPC), and specifically, by the following examples. The value measured by the method described.

The acid value of the dye multimer is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, further preferably 27 mgKOH/g or more, and particularly preferably 30 mgKOH/g or more. Further, the upper limit of the acid value is preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less, further preferably 180 mgKOH/g or less, particularly preferably 130 mgKOH/g or less, and further preferably 120 mgKOH/g. the following. By satisfying the above range, the developability is further improved, so that the development residue can be further reduced.

The curable base value of the dye multimer is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and still more preferably 0.3 mmol/g or more. When the curable base value is 0.1 mmol/g or more, a cured film excellent in light resistance or solvent resistance can be easily obtained. In addition, fading of the film caused by the developer, the stripper, or the like can be more effectively suppressed. The upper limit of the curable base value is not particularly limited, and is, for example, preferably 2.0 mmol/g or less, more preferably 1.5 mmol/g or less. The curable base value can be calculated by dividing the number of curable groups introduced into the dye multimer by the molecular weight of the dye multimer. Further, it can be actually measured by an analysis means such as ¹ H-NMR (nuclear magnetic resonance).

The dye multimer of the present invention can be used for applications such as color filters, inks (for inkjet, printing, etc.), paints, and light-shielding films.

<Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention is obtained by using the coloring composition of the present invention as described above. The color filter of the present invention can be used in a solid-state imaging device such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS), or an image display device.

The coloring pattern (coloring pixel) of the color filter of the present invention has a film thickness of preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more. Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.

<Pattern forming method> The pattern forming method of the present invention includes the step of forming a colored composition layer on the support using the coloring composition of the present invention; and patterning the colored composition layer by photolithography or dry etching A step of.

The pattern formation by the photolithography method preferably includes a step of forming a colored composition layer on the support using the colored composition, a step of exposing the colored composition layer in a pattern, and developing the unexposed portion. The step of removing the pattern to form. A step of baking the colored composition layer (prebaking step) and a step of baking the developed pattern (post-baking step) may be provided as needed. Further, the pattern formation by the dry etching method preferably includes a step of forming a colored composition layer on the support using a colored composition, and hardening to form a cured layer; and forming a photoresist layer on the cured layer. a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and a step of dry etching the cured layer to form a pattern using the resist pattern as an etch mask . Hereinafter, each step will be described.

<<Step of Forming Colored Composition Layer>> In the step of forming the curable composition layer, a colored composition layer is formed on the support using the colored composition.

As the support, for example, a substrate for a solid-state imaging device in which a solid-state imaging device (light receiving element) such as a CCD or a CMOS is provided on a substrate (for example, a germanium substrate) can be used. The pattern of the present invention can be formed on the surface side (surface) on which the solid-state image sensor is formed on the solid-state image sensor substrate, or on the surface side (back surface) on which the solid-state image sensor is not formed. On the support, an undercoat layer may be provided as needed to improve adhesion to the upper layer, prevent diffusion of substances, or achieve planarization of the substrate surface.

As a method of applying the coloring composition on the support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

The colored composition layer formed on the support can be dried (prebaked). In the case where the pattern is formed by a low temperature process, prebaking may not be performed. In the case of prebaking, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and still more preferably 110 ° C or lower. The lower limit can be, for example, 50 ° C or higher, or 80 ° C or higher. By carrying out the prebaking temperature of 150 ° C or lower, for example, in the case of using a photoelectric conversion film of an image sensor using an organic material, these characteristics can be more effectively maintained. The prebaking time is preferably from 10 seconds to 300 seconds, more preferably from 40 seconds to 250 seconds, and further preferably from 80 seconds to 220 seconds. Drying can be carried out using a hot plate, an oven or the like.

(When Patterning is Performed by Photolithography) <<Exposure Step>> Next, the colored composition layer is exposed in a pattern (exposure step). For example, an exposure device such as a stepper can be used to expose the colored composition layer by a mask having a predetermined mask pattern, whereby pattern exposure can be performed. Thereby, the exposed portion can be hardened. As the radiation (light) which can be used for exposure, ultraviolet rays (particularly i-rays) such as g-rays and i-rays can be preferably used. The irradiation amount (exposure amount) is, for example, preferably 0.03 J/cm ² to 2.5 J/cm ² , more preferably 0.05 J/cm ² to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and exposure can be performed in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, and substantially oxygen-free) having an oxygen concentration of 19% by volume or less, in addition to exposure in the atmosphere. Exposure can also be carried out in a high oxygen environment (for example, 22% by volume, 30% by volume, and 50% by volume) in which the oxygen concentration exceeds 21% by volume. Further, the exposure illuminance can be appropriately set, and can be usually selected from the range of 1000 W/m ² to 100000 W/m ² (for example, 5000 W/m ² , 15000 W/m ² , and 35000 W/m ² ). The oxygen concentration and the exposure illuminance can be combined under suitable conditions, and for example, the oxygen concentration is 10% by volume, the illuminance is 10000 W/m ² , the oxygen concentration is 35% by volume, and the illuminance is 20,000 W/m ² . The film thickness of the cured film is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more. By setting the film thickness to 2.0 μm or less, high resolution and high adhesion can be easily obtained.

<<Developing Step>> Next, the unexposed portion is developed and removed to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the colored composition layer of the unexposed part in the exposure step is eluted into the developing solution, and only the portion where the light is hardened remains. As the developer, an organic alkaline developer which does not damage the solid image sensor or the circuit of the substrate is preferable. The temperature of the developer is, for example, preferably 20 ° C to 30 ° C. The development time is preferably from 20 seconds to 180 seconds. Further, in order to improve the residue removal property, the following steps may be repeated several times: the developer is removed every 60 seconds, and a new developer is supplied.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydrogen. Tetrabutylammonium oxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4. 0] Organic basic compound such as 7-undecene. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water can be preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass. Further, an inorganic base can also be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate or the like is preferable. Further, a surfactant may be used in the developer. Examples of the surfactant include a surfactant described in the curable composition, and a nonionic surfactant is preferred. Further, in the case of using a developer containing such an aqueous alkaline solution, it is preferred to carry out washing (rinsing) with pure water after development.

It is also possible to carry out heat treatment (post-baking) after development and after drying. Post-baking is a heat treatment after development for completely hardening the film. In the case of post-baking, the post-baking temperature is, for example, preferably from 100 ° C to 240 ° C. From the viewpoint of film hardening, it is more preferably from 200 ° C to 230 ° C. In the case where an organic electroluminescence (organic luminescence) element is used as the illuminating light source or when the photoelectric conversion film of the image sensor is formed of an organic material, the post-baking temperature is preferably 150° C. or less. More preferably, it is 120 ° C or less, more preferably 100 ° C or less, and particularly preferably 90 ° C or less. The lower limit can be, for example, 50 ° C or higher. The film after development may be post-baked by a continuous or batch type using a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high frequency heater. Further, in the case of forming a pattern by a low-temperature process, post-baking may not be performed.

(When Patterning is Performed by Dry Etching) Patterning by dry etching can be performed by hardening a colored composition layer formed on a support to form a cured layer, and then A patterned photoresist layer is formed on the obtained cured layer, and the photoresist layer is etched using an etching gas as a mask. Specifically, it is preferred to apply a positive or negative radiation sensitive composition onto the cured layer and dry it, thereby forming a photoresist layer. In the formation of the photoresist layer, it is preferred to carry out the prebaking treatment. In particular, as a forming process of the photoresist, it is preferable to perform a heat treatment after exposure and a heat treatment (post-baking treatment) after development.

As the photoresist layer, for example, a sense of positive type such as induced ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays can be preferably used. Radiation linear composition. In the radiation, g rays, h rays, and i rays are preferable, and among them, i rays are preferable. Specifically, the positive radiation sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is obtained by decomposing a quinonediazide group by light irradiation at a wavelength of 500 nm or less and generating a carboxyl group, and the result is changed from an alkali-insoluble state to a base. Soluble. Since this positive type resist is remarkably excellent in resolving power, it is used for the production of an integrated circuit such as an integrated circuit (IC) or a large scale integrated circuit (LSI). As the quinonediazide compound, a naphthoquinonediazide compound can be mentioned. As a commercial item, "FHi622BC" (made by Fujifilm Electronics Materials Co., Ltd.), etc. are mentioned, for example.

The thickness of the photoresist layer is preferably from 0.1 μm to 3 μm, more preferably from 0.2 μm to 2.5 μm, still more preferably from 0.3 μm to 2 μm. Further, the method of applying the positive radiation sensitive composition can be preferably carried out by using the coating method of the colored composition.

Then, the photoresist layer is exposed and developed, thereby forming a resist pattern (patterned photoresist layer) provided with a resist through-hole group. The formation of the resist pattern is not particularly limited, and can be suitably performed by optimizing a conventionally known photolithography technique. A resist through-hole group is provided on the photoresist layer by exposure and development, whereby a resist pattern as an etching mask used in the subsequent etching is provided on the cured layer.

The exposure of the photoresist layer can be carried out by interposing a predetermined mask pattern, using g-rays, h-rays, i-rays, etc., preferably an i-ray alignment type or a negative type radiation sensitive composition. Implement exposure. After the exposure, the developing treatment is performed by the developing solution, whereby the photoresist is removed in combination with the region where the colored pattern is to be formed.

As the developer, any developer can be used as long as it does not affect the cured layer and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various solvents or an aqueous alkaline solution can be used. The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound in a concentration of from 0.001% by mass to 10% by mass, preferably from 0.01% by mass to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and the like. Further, in the case of using an alkaline aqueous solution, the cleaning treatment is usually carried out using water after development.

Next, the resist pattern was used as an etching mask, and patterned by dry etching so that a through-hole group was formed on the cured layer.

As the dry etching, from the viewpoint of forming a pattern cross section more rectangularly or further reducing damage to the support, it is preferably carried out by the following method. Preferably, the method includes etching using a mixed gas of a fluorine-based gas and oxygen (O ₂ ), and etching in a first step until a region (depth) in which the support is not exposed; in the first stage After the etching, etching is performed using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) until it is preferably in the vicinity of the region (depth) where the support is exposed; and after the support is exposed Over etching. Hereinafter, a specific method of dry etching, etching in the first stage, etching in the second stage, and over etching will be described.

Dry etching is performed by previously obtaining etching conditions by the following method. (1) The etching rate (nm/min) in the etching in the first step and the etching rate (nm/min) in the etching in the second step were respectively calculated. (2) The time during which the desired thickness is etched by the first-stage etching and the time during which the desired thickness is etched by the second-stage etching are respectively calculated. (3) The first-stage etching is performed in accordance with the etching time calculated in the above (2). (4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the etching time may be determined by endpoint detection, and the second etching may be performed in accordance with the determined etching time. (5) The over-etching time is calculated with respect to the total time of the above (3) and (4), and over-etching is performed.

The mixed gas used in the etching step of the first step preferably contains a fluorine-based gas and oxygen (O ₂ ) from the viewpoint of processing the organic material as the film to be processed into a rectangular shape. Further, the damage of the support can be avoided by etching in the etching step of the first step until the region where the support is not exposed. In addition, in the etching step of the first step, etching is performed by using a mixed gas of a fluorine-based gas and oxygen gas until the support is not exposed, and the second step of the etching step and excessive is considered from the viewpoint of avoiding damage of the support. The etching step is preferably performed by using a mixed gas of nitrogen gas and oxygen gas.

The ratio of the amount of etching in the etching step in the first step to the amount of etching in the etching step in the second step is determined in such a manner that the rectangularity formed by the etching treatment in the etching step of the first step is not impaired. Further, the ratio of the latter in the total etching amount (the total of the etching amount in the etching step in the first step and the etching amount in the etching step in the second step) is preferably in a range of more than 0% and not more than 50%. More preferably, it is 10% to 20%. The amount of etching refers to an amount calculated from the difference between the film thickness remaining in the film to be etched and the film thickness before etching.

In addition, the etching preferably includes an overetching process. The overetching treatment is preferably performed after setting the overetching ratio. Further, the overetching ratio is preferably calculated based on the time of the etching process that is initially performed. The over-etching ratio can be arbitrarily set. However, in terms of maintaining the etching resistance of the photoresist and the rectangularity of the etched pattern, it is preferably 30% or less, more preferably 5%, of the etching treatment time in the etching step. ~25%, especially good 10% to 15%.

Then, the resist pattern remaining after the etching (ie, the etching mask) is removed. The removal of the resist pattern preferably includes a step of imparting a stripping liquid or a solvent onto the resist pattern and forming a state in which the resist pattern can be removed, and a step of removing the resist pattern using the washing water.

As a step of applying a peeling liquid or a solvent to the resist pattern and forming a state in which the resist pattern can be removed, for example, a stripping liquid or a solvent is applied to at least the resist pattern and stays for a predetermined period of time. To carry out the step of liquid-covering development. The time for leaving the stripping solution or solvent to stay is not particularly limited, but is preferably from several tens of seconds to several minutes.

Further, as a step of removing the resist pattern using the washing water, for example, a step of removing the resist pattern by spraying the washing water onto the resist pattern from the spray type or the spray type spray nozzle is exemplified. Pure water can be preferably used for the washing water. Further, examples of the injection nozzle include an injection nozzle in which the entire support body is included in the injection range, or an injection nozzle which is a movable injection nozzle and whose movable range includes the entire support body. In the case where the ejection nozzle is movable, in the step of removing the resist pattern, the cleaning water is sprayed twice or more from the center of the support to the end of the support, thereby more effectively removing the resist. Agent pattern.

The stripper usually contains an organic solvent and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether-based compound or an acetal-based compound, 5) a ketone-based compound or an aldehyde-based compound, and 6) An ester compound, 7) a polyol compound, 8) a carboxylic acid compound or an acid anhydride compound thereof, 9) a phenol compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. The stripping liquid preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, and the like. Diethanolamine, triethanolamine or the like is preferably monoethanolamine, diethanolamine or triethanolamine, more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α. -methylpyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrole Pyridine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-lutidine, etc., preferably N-methyl-2-pyrrole Iridone, N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as an acyclic nitrogen-containing compound, and As the cyclic nitrogen-containing compound, at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine preferably further contains monoethanolamine and N-methyl-2-pyrrolidone.

When the removal is performed by the stripping solution, the resist pattern formed on the pattern may be removed, and even if the deposited matter as an etching product adheres to the sidewall of the pattern, it may not be completely removed. Sediment. The term "deposit" means that the etching product adheres and accumulates on the side wall of the hardened layer.

The content of the acyclic nitrogen-containing compound is preferably 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the peeling liquid, and the content of the cyclic nitrogen-containing compound is 65 parts by mass based on 100 parts by mass of the peeling liquid. More than 70 parts by mass or less. Further, the peeling liquid is preferably obtained by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

<Solid-State Imaging Element> The solid-state imaging element of the present invention has the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration in which the color filter of the present invention is provided as a solid-state imaging device, and the following configuration is exemplified.

The solid-state imaging device has a configuration in which a plurality of photodiodes (photodiodes) constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a polycrystalline germanium or the like are provided on the support. The transmission electrode has a light-shielding film containing tungsten or the like which is open only in the light-receiving portion of the photodiode, and has a light-shielding film covering the entire surface of the light-shielding film and light-receiving light reception on the light-receiving film. A device protective film comprising tantalum nitride or the like formed in a portion manner, and the color filter of the present invention is provided on the device protective film. Furthermore, it may be configured on the device protective film and under the color filter (on the side close to the support) to have a condensing mechanism (for example, a microlens or the like. The same applies hereinafter) or on the color filter. The composition of the concentrating mechanism, and the like.

<Image Display Device> The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device. The image display device including the color filter of the present invention can display a high-quality image, and the display image of the high-quality image has good color tone and excellent display characteristics. The definition of the display device or the details of each display device is described, for example, in "Electronic display devices (Sasaki Sasaki, Industrial Research Association, shares issued in 1990)", "Display devices (Ibuki Shunzhang, Industrial Books ( Shares), issued in 1989) and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Editor Uchida Ryuo, Industrial Research Association, issued in 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, a plurality of types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

The color filter of the present invention can also be used in a liquid crystal display device of a Thin Film Transistor (TFT) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to a liquid crystal display having an enlarged viewing angle such as a transverse electric field driving method such as In Plane Switching (IPS) or a pixel division method such as Multi-domain Vertical Alignment (MVA). Device, or Super-Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), on-chip spacer (OCS), fringe field switching (fringe field switching, FFS), and Reflective Optically Compensated Bend (R-OCB). In addition, the color filter of the present invention is also available in a Color-Filter On Array (COA) mode. These image display methods are described, for example, in "EL, Plasma Display Panel (PDP), Liquid Crystal Display (LCD) Display - Technology and Market Trends - (Dongli Research Center) (Toray Research Center, Research and Research Department, issued in 2001), page 43 et al.

The liquid crystal display device including the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. For example, the "94 liquid crystal display peripheral materials and chemicals market (Ichishima Kentaro, CMC (share), issued in 1994)", "2003 liquid crystal related market status and future prospects (volume) (Former Liangji, Fuji Kamelai Institute (share), issued in 2003). The backlight is described in "The Society for Information Display (Meeting Digest)" 1380 (2005) (A. Konno et al.) or "Monthly Display" 2005. The 18th to 24th pages of the December issue (Island Kangyu), the 25th and 30th pages of the document (Yamamu Longming), etc. [Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are the quality standards. Further, in the following structural formula, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ts represents a toluenesulfonyl group.

<Measurement of Weight Average Molecular Weight> The weight average molecular weight can be measured by a polystyrene equivalent value measured by gel permeation chromatography (GPC). Column type: The column with TOSOH TSKgel Super HZM-H and TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 is developed. Solvent: tetrahydrofuran column temperature: 40 °C flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass) Device name: HLC-8220GPC manufactured by Tosoh: Ref. Refractive Index (RI) Detector Calibration Curve Base Resin: Polystyrene

<Synthesis Example> (Synthesis Example 1) Synthesis of Pigment Monomeric (X-1)

[化50]

28.8 g of Compound a was added to 200 mL of dehydrated tetrahydrofuran and cooled to -50 °C. Next, 128 mL of 1.6 mol/L n-butyllithium (hexane solution) was added dropwise and the temperature was raised to -5 °C to 0 °C. Next, 45.4 g of ethyl iodide was slowly added thereto, and the temperature was raised to 30 °C. Next, 100 mL of water was added, and the mixture was separated with 200 mL of ethyl acetate. The oil layer was washed twice with 100 mL of water, and the oil layer was concentrated, whereby Intermediate b 33.2 g was obtained. Next, 30.0 g of the intermediate b, 16.0 g of p-chloromethylstyrene, 1.0 g of magnesium oxide, 80 mL of tetrahydrofuran, and 20 mL of ion-exchanged water were mixed, and the mixture was heated at 100 ° C for 2 hours. After standing to cool to room temperature, sodium N,N bis(trifluoromethanesulfonyl) sulfimine 31.1 g was added and stirred for 1 hour. After adding 100 mL of ethyl acetate and 100 mL of 1 mol/L hydrochloric acid and separating the liquid, the oil layer was washed with 100 mL of water. After the oil layer was concentrated, it was purified by column chromatography using silica gel to obtain 22.5 g of a pigment monomer (X-1).

(Synthesis Example 2) Synthesis of a pigment single body (X-2) [Chem. 51]

Except that the p-chloromethylstyrene of Synthesis Example 1 was changed to ethyl iodide, the same operation was carried out to obtain Intermediate d. Further, the intermediate c is synthesized in the same manner as the method described in paragraph 0372 of JP-A-2015-30742. 11.2 g of Intermediate c and 10.0 g of Intermediate d were stirred in dichloromethane (200 mL) at room temperature for 2 hr. Next, 100 mL of water was added and liquid separation was carried out. After concentrating the oil layer, it was purified by column chromatography using tannin to obtain a pigment single amount (X-2) of 15.5 g.

(Synthesis Example 3) Synthesis of a pigment single body (X-3) [Chem. 52]

28.8 g of Compound a was added to 200 mL of dehydrated tetrahydrofuran and cooled to -50 °C. Next, 128 mL of 1.6 mol/L n-butyllithium (hexane solution) was added dropwise and the temperature was raised to -5 °C to 0 °C. Next, 70.0 g of the compound e was slowly added, and the temperature was raised to 30 °C. Next, 100 mL of water was added, and the mixture was separated with 200 mL of ethyl acetate. The oil layer was washed twice with 100 mL of water, and the oil layer was concentrated, whereby Compound f 54.1 g was obtained. Next, 50.0 g of the compound f, 30.0 g of dimethyl sulfate, and 1.0 g of magnesium oxide were heated at 80 ° C for 20 hours in 80 mL of tetrahydrofuran and 20 mL of ion-exchanged water. After standing to cool to room temperature, sodium N,N bis(trifluoromethanesulfonyl) sulfimine 31.1 g was added and stirred for 1 hour. After adding 100 mL of ethyl acetate and 100 mL of 1 mol/L hydrochloric acid and separating the liquid, the oil layer was washed with 100 mL of water. After concentrating the oil layer, it was purified by column chromatography using tannin to obtain 15.4 g of a pigment monomer (X-3).

(Synthesis Example 4) Synthesis of a pigment single body (X-4) [Chem. 53]

30.4 g of compound g was added to 200 mL of dehydrated tetrahydrofuran and cooled to -50 °C. Next, 128 mL of 1.6 mol/L n-butyllithium (hexane solution) was added dropwise and the temperature was raised to -5 °C to 0 °C. Next, 22.7 g of ethyl iodide was slowly added thereto, and the temperature was raised to 30 °C. Next, 100 mL of water was added, and the mixture was separated with 200 mL of ethyl acetate. The oil layer was washed twice with 100 mL of water, and the oil layer was concentrated, whereby intermediate h 31.9 g was obtained. Next, 3 h of the intermediate h, 16.0 g of p-chloromethylstyrene, 1.0 g of magnesium oxide, 80 mL of tetrahydrofuran, and 20 mL of ion-exchanged water were mixed, and the mixture was heated at 100 ° C for 2 hours. After standing to cool to room temperature, sodium N,N bis(trifluoromethanesulfonyl) sulfimine 31.1 g was added and stirred for 1 hour. After adding 100 mL of ethyl acetate and 100 mL of 1 mol/L hydrochloric acid and separating the liquid, the oil layer was washed with 100 mL of water. After concentrating the oil layer, it was purified by column chromatography using silica gel to obtain 16.2 g of a pigment monomer (X-4).

(Synthesis Example 5) Synthesis of a pigment single body (X-5) [Chem. 54]

26.8 g of the compound i, 30.0 g of the compound 1), 1.0 g of magnesium oxide, 80 mL of tetrahydrofuran, and 20 mL of ion-exchanged water were mixed, and the mixture was heated at 100 ° C for 2 hours. After standing to cool to room temperature, sodium N,N bis(trifluoromethanesulfonyl) sulfimine 31.1 g was added and stirred for 1 hour. After adding 100 mL of ethyl acetate and 100 mL of 1 mol/L hydrochloric acid and separating the liquid, the oil layer was washed with 100 mL of water. After concentrating the oil layer, it was purified by column chromatography using silica gel to obtain 19.7 g of a pigment monomer (X-5).

(Synthesis Example 6) Synthesis of a pigment single body (X-6) [Chem. 55]

A dye single amount (X-6) of 14.9 g was obtained by the same operation as in Synthesis Example 2 except that the intermediate d of the synthesis example 2 was changed to basic yellow 1.

(Synthesis Example 7) Synthesis of a pigment single body (X-7) [Chem. 56]

The same operation was carried out except that the compound 1) of Synthesis Example 5 was changed to 2-bromoethanol to obtain 12.1 g of a pigment monomer (X-7).

(Synthesis Example 8) Synthesis of Pigment Polymer (S-1) [Chem. 57]

Monomeric substance (X-1) (16.4 g), methacrylic acid (3.00 g), dodecyl mercaptan (0.51 g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA (Propylene glycol monomethyl ether acetate)" (46.6 g) was mixed, and a half of the mixture was added to a three-necked flask, and heated to 80 ° C under a nitrogen atmosphere. To the remaining solution, 2,2'-azobis(isobutyrate) dimethyl ester (trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.58 g) was added and dissolved, and it took 2 hours. It was added dropwise to a three-necked flask. After stirring for 3 hours, the temperature was raised to 90 ° C and stirred under heating for 2 hours. Next, glycidyl methacrylate (1.60 g) and tetrabutylammonium bromide (0.10 g) were added, and the mixture was heated at 90 ° C for 10 hours. After cooling to room temperature, it was added dropwise to a mixed solvent of methanol/ion exchanged water = 100 mL/10 mL, and then reprecipitated. The obtained solid was dispersed in hexane / ethyl acetate = 90 mL / 10 mL and filtered. After the obtained solid was air-dried at 40 ° C for 2 days, 14.2 g of a dye multimer (S-1) was obtained.

(Synthesis Example 9) Pigment Polymer (S-2) The same procedure as in Synthesis Example 8 was carried out except that the pigment monomer (X-1) was changed to the dye polymer (X-2). Polymer (S-2).

(Synthesis Example 10) Pigment Polymer (S-3) The same procedure as in Synthesis Example 8 was carried out except that the pigment monomer (X-1) was changed to the dye polymer (X-4). Polymer (S-3).

(Synthesis Example 11) Pigment Multimer (S-4) The same procedure as in Synthesis Example 8 was carried out except that the dye monomer (X-1) was changed to the dye polymer (X-5). Polymer (S-4).

(Synthesis Example 12) Pigment Polymer (S-5) The same procedure as in Synthesis Example 8 was carried out except that the pigment monomer (X-1) was changed to the dye polymer (X-6). Polymer (S-5).

(Synthesis Example 13) Synthesis of Pigment Multimer (S-6) [Chem. 58] Compound (X-3) 9.1 g (13.5 mmol), 1,1-bis(hydroxymethyl)propionic acid 2.2 g (16.5 mmol), 2,3-dihydroxypropyl methacrylate 6.3 g (39.1 mmol) 1,6-diisocyanatohexane 11.6 g (69.1 mmol) and Neostarn U-1000 (0.1 g) were added to 100 g of methyl ethyl ketone under nitrogen at 80 ° C Heat for 10 hours. After cooling to room temperature, it was added to 1000 mL of hexane, and the obtained gelatinous substance was transferred to a Petri dish, and air-dried at 40 ° C for 2 days, thereby obtaining a pigment multimer (S-6) 20.4. g.

(Synthesis Example 14) Synthesis of Pigment Multimer (S-7) [Chem. 59] 11.9 g (24.7 mmol) of compound (X-7) and 2.7 g (12.4 mmol) of pyromellitic anhydride were added to 50 g of PGMEA, and the mixture was heated under reflux for 10 hours under a nitrogen atmosphere. After cooling to room temperature, it was added to 1000 mL of hexane, and the obtained solid was filtered, and air-dried at 40 ° C for 2 days, thereby obtaining 17.5 g of a dye multimer (S-7).

(Synthesis Example 15) Synthesis of Pigment Multimer (S-8) [Chem. 60]

Under a nitrogen atmosphere, 3.0 g of dipentaerythritol hexakis(6-mercaptohexanoate), 12.0 g of a pigment monomer (X-1), and 30 g of N-methylpyrrolidone were heated at 80 °C. Next, 2,2'-azobis(isobutyrate) dimethyl ester (trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.) (0.3 g) was added and heated for 7 hours. After standing to cool, 2.0 g of methacrylic acid, 1.0 g of 2-(2-bromo-2-methylpropenyl)ethyl methacrylate, and 2,2'-azobis(isobutyrate) dimethyl ester were added. 0.2 g. The solution was added dropwise to 5 g of N-methylpyrrolidone heated at 80 ° C under a nitrogen atmosphere for 1 hour, stirred for 3 hours, and then left to cool. To the solution, 2.0 g of Diazabicyclo undecene (DBU) was added and stirred for 12 hours, and then 2.0 g of methanesulfonic acid was added. The obtained solution was added dropwise to a solution of methanol 250 mL/water 250 mL. The obtained solid was filtered and dried, whereby a pigment multimer (S-8) 11.1 g was obtained.

[Table 1] Further, MMA in the table means methacrylic acid, GMA means glycidyl methacrylate, HMP means 1,1-bis(hydroxymethyl)propionic acid, and GLM means 2,3-dihydroxypropyl methacrylate. PA represents pyromellitic anhydride, and MBMP represents 2-(2-bromo-2-methylpropionyl)ethyl methacrylate.

<Test Example 1> Pattern formation by photolithography (Preparation of resist liquid for undercoat layer) The following components were mixed and dissolved to prepare a resist liquid for an undercoat layer. - Composition of the resist liquid for the undercoat layer - Solvent (PGMEA): 19.20 parts, solvent (ethyl lactate): 36.67 parts, alkali-soluble resin (benzyl methacrylate/methacrylic acid/methacrylic acid-2) -Hydroxyethyl ester copolymer (mole ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) of 40% PGMEA solution): 30.51 parts, hardening compound (dipentaerythritol hexaacrylate, Kyala) (KAYARAD) DPHA (manufactured by Nippon Kayaku Co., Ltd.): 12.20 parts, polymerization inhibitor (p-methoxyphenol): 0.0061 parts, fluorine-based surfactant (Megafac F475, manufactured by Diane Health (DIC)) : 0.83 parts・Photopolymerization initiator (trihalomethyltriazine photopolymerization initiator, TAZ-107, manufactured by Green Chemical): 0.586 parts

(Preparation of ruthenium wafer substrate with undercoat layer) A ruthenium wafer having a diameter of 6 Å (1 Å = 25.4 mm) was heat-treated at 200 ° C for 30 minutes in an oven. Then, the undercoat layer resist liquid is applied onto the tantalum wafer so as to have a dry film thickness of 1.5 μm, and further dried in an oven at 220 ° C for 1 hour to form an undercoat layer. A tantalum wafer substrate with an undercoat layer is obtained.

(Preparation of Colored Composition) <<Preparation of Pigment Dispersion 1>> A pigment dispersion liquid 1 was prepared in the following manner. By using a beads mill (diameter of zirconia beads of 0.3 mm), containing 13.0 parts of CI Pigment Green 36 (green pigment, average particle size of 55 nm), and 5.0 parts of a pigment dispersant (di A mixture of Disperbyk-111 (manufactured by BYK Chemie) and 82.0 parts of PGMEA was mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) equipped with a pressure reducing mechanism was used, and dispersion treatment was carried out at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times to obtain a pigment dispersion liquid 1 (pigment concentration: 13%). With respect to the obtained pigment dispersion liquid 1, the particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and it was 24 nm.

<<Preparation of Pigment Dispersion Liquid 2>> In the pigment dispersion liquid 1, a pigment dispersion liquid 2 was prepared in the same manner as the pigment dispersion liquid 1, except that C.I. Pigment Red 254 was used instead of C.I. Pigment Green 36. The pigment dispersion 2 has a particle size of 26 nm.

<<Preparation of Pigment Dispersion Liquid 3>> In the pigment dispersion liquid 1, a pigment dispersion liquid 3 was prepared in the same manner as the pigment dispersion liquid 1, except that C.I. Pigment Green 58 was used instead of C.I. Pigment Green 36. The pigment dispersion 3 had a particle size of 29 nm.

<<Preparation of Pigment Dispersion 4>> In the pigment dispersion liquid 1, a pigment dispersion liquid 4 was prepared in the same manner as the pigment dispersion liquid 1, except that C.I. Pigment Green 59 was used instead of C.I. Pigment Green 36. The pigment dispersion 4 has a particle size of 24 nm.

<Preparation of Colored Composition> Each of the following components was mixed, dispersed, dissolved, and filtered through a 0.45 μm nylon filter to obtain a colored composition. - Composition - ・Pigment (Compound described in the following table): 0.040 parts by weight of solid content ・Pigment dispersion containing pigment described in the following table (pigment concentration: 13.0%): 0.615 parts · Cyclohexanone: 100 parts alkali-soluble resin (J1 or J2: compounds described in the following table): 5 parts · Solsperse 20000 (1% cyclohexane solution, manufactured by Lubrizol, Japan) ): 1 part of photopolymerization initiator (the following (I-1) to (I-8): the compound described in the following table): 1 part, curable compound (dipentaerythritol hexaacrylate, Kyala) (KAYARAD) DPHA (manufactured by Nippon Kayaku Co., Ltd.): 10 parts glycerol propoxylate (1% cyclohexane solution): 0.1 part

Photopolymerization initiator: The following structure. The following (I-1) is IRGACURE (registered trademark)-OXE01, (I-2) is IRGACURE (registered trademark)-OXE02 (manufactured by BASF), (I- 3) IRGACURE (registered trademark)-379 and (I-4) are DAROCUR (registered trademark)-TPO (all of which are manufactured by BASF). In the following structural formula, Ph represents a phenyl group. [化61]

Alkali-soluble resin: the following structure [Chem. 62]

Pigment XH-1: the following structure [Chem. 63]

(Production of Color Filter) Each of the colored compositions prepared above was applied onto the undercoat layer of the underlying coated germanium wafer substrate to form a composition layer (coating film). The coating amount of the colored composition was set to a coating amount of a dry film thickness of 0.6 μm. Next, the coating film was subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 °C. The prebaked substrate was placed at room temperature (over time) for 24 hours.

Then, using an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon), an island pattern mask having a pattern of 1.0 μm square was applied at a wavelength of 365 nm, at 50 mJ/cm ² . Exposure was performed at various exposures of 1200 mJ/cm ² . After that, the substrate on which the exposed film was formed was placed on a horizontal rotary table of a rotary/spray developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji film electronic material (Fujifilm) was used. Fabrication) was carried out at 23 ° C for 60 seconds for liquid-coated development to form a colored pattern.

The substrate on which the colored pattern is formed is fixed on the horizontal rotating table by a vacuum chuck method, and the silicon wafer substrate is rotated by a rotating device at a rotation speed of 50 rpm, and is self-ejection nozzle from above the center of rotation thereof. The pure water is supplied in a shower form to perform a rinsing treatment, and then spin-dried. By the above manner, a color filter having a colored pattern is produced. The size of the colored pattern was measured using a scanning electron microscope (SEM) "S-9260A" (manufactured by Hitachi High-Technologies). The exposure amount in which the pattern size is 1.0 μm is set as the optimum exposure amount.

(Performance Evaluation) <Color unevenness> The colored composition was applied onto a glass substrate to form a coating film. The coating amount of the colored composition was set to a coating amount of a dry film thickness of 0.7 μm. Next, the coating film was subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 °C. After allowing to stand at room temperature for 24 hours, a sample (a glass substrate with a colored layer) was produced by performing exposure in the same manner as in the method of producing a color filter, except that no mask was used. The luminance distribution of the sample was measured by the following method, and the color unevenness was evaluated based on the ratio of the pixel within ±5% of the deviation from the average level to the total number of pixels. The method for measuring the luminance distribution was carried out by using an image of a sample taken with a microscope MX-50 (manufactured by Olympus Co., Ltd.). Further, in the luminance distribution, the luminance having the largest number of pixels is defined as the average luminance. The ratio (%) of the pixel within ±5% of the deviation from the average level is described in the color unevenness column of the following table.

<Pattern Shape> The pattern shape of the obtained color filter was observed by SEM (scanning electron microscope). A: Unpatterned skew or rough surface. B: There is a pattern skew or a rough surface, which is problematic in practical use.

<Pattern defect> 200 patterns were observed by SEM, and the presence or absence of a pattern defect was confirmed. The more pattern defects, the more adversely the yield. The number of pattern defects generated is described in the following table.

<Defect> Each coloring composition was applied onto the undercoat layer of the underlying coated germanium wafer substrate to form a coating film. The coating amount of the colored composition was set to a coating amount of a dry film thickness of 0.6 μm. Next, the coating film was subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 °C. After the substrate was allowed to stand at room temperature (over time) for 24 hours, the number of defects (number/cm ² ) was measured using a ComPlus manufactured by Applied Materials. The fewer the number of defects, the better. [Table 2]

As is clear from the above table, the coloring composition of the example can suppress the occurrence of color unevenness and defects even after passing through the prebaking. Further, the pattern shape is good and the pattern defect is small. On the other hand, the color unevenness and the defect of the comparative example were inferior. Further, the pattern shape is poor and the pattern is defective.

Further, PG36 in the table is a shorthand for C.I. Pigment Green 36. Further, PG254 is a shorthand for C.I. Pigment Red 254. In addition, PG58 is a shorthand for C.I. Pigment Green 58. In addition, PG59 is a shorthand for C.I. Pigment Green 59.

In the coloring composition of the example, the same result can be obtained as the curable compound, even if dipentaerythritol hexaacrylate is changed to A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) of the same quality.

<Test Example 2> Pattern formation by dry etching method (Preparation of colored composition) The following components were mixed and dissolved to obtain a colored composition. - Composition - - Cyclohexanone: 1.133 parts / Pigment (compound described in the following table): 0.040 parts by weight of the solid content, and a pigment dispersion liquid (pigment concentration: 13.0%) containing the pigments described in the following table: 0.615 parts·hardening compound (EHPE-3150 (made by Daicel), 1,2-epoxy-4-(2-) of 2,2-bis(hydroxymethyl)-1-butanol Ethylene oxide based cyclohexane adduct)): 0.070 parts glycerol propoxylate (1% cyclohexane solution): 0.048 parts

(Production of Color Filter) The colored composition was applied onto a glass substrate by a spin coater so that the film thickness was 0.6 μm, and heat treatment was performed for 120 seconds using a hot plate at 100 ° C (pre- bake). After leaving it at room temperature for 24 hours, it was then subjected to heat treatment (post-baking) for 300 seconds using a hot plate at 220 ° C to prepare a cured film. A positive photoresist "FHi622BC" (manufactured by Fujifilm Electronics Materials) was applied onto the cured film, and prebaking was performed to form a photoresist layer having a film thickness of 0.8 μm. Then, using a i-ray stepper (manufactured by Canon), the photoresist layer was subjected to pattern exposure at an exposure amount of 350 mJ/cm ² , at a temperature at which the temperature of the photoresist layer or the ambient temperature became 90 ° C. Heat treatment was carried out for 1 minute. Thereafter, the photoresist stripping liquid "MS230C" (manufactured by Fujifilm Electronics Materials) was used, and the resist pattern was removed by a peeling treatment for 120 seconds, and further, washing with pure water and spin drying were performed. Thereafter, a dehydration baking treatment was performed at 100 ° C for 2 minutes. Next, dry etching was performed by the following procedure.

Using a dry etching device (manufactured by Hitachi High-Technologies, U-621), the radio frequency (RF) power was set to 800 W, the antenna bias was set to 400 W, and the wafer bias was set. 200 W, the internal pressure of the reaction chamber was set to 4.0 Pa, the substrate temperature was set to 50 ° C, and the gas type and flow rate of the mixed gas were set to CF ₄ : 80 mL / min., O ₂ : 40 mL / min. Ar: 800 mL/min., and the first stage etching treatment was performed for 80 seconds.

Then, in the same etching chamber, the RF (high frequency) power was set to 600 W, the antenna bias was set to 100 W, the wafer bias was set to 250 W, and the internal pressure of the reaction chamber was set to 2.0 Pa. The substrate temperature was set to 50 ° C, and the gas type and flow rate of the mixed gas were set to N ₂ :500 mL/min., O ₂ :50 mL/min., Ar:500 mL/min. (N ₂ /O ₂ /Ar=10/1/10), the second-stage etching treatment and the over-etching treatment were performed for 28 seconds.

After performing the dry etching under the above conditions, the photoresist stripping liquid "MS230C" (manufactured by Fujifilm Electronics Materials) was used, and the resist was removed by a peeling treatment for 120 seconds to further remove the resist. Cleaning, spin drying. Thereafter, a dehydration baking treatment was performed at 100 ° C for 2 minutes.

(Performance Evaluation) Color unevenness, pattern shape, pattern defect, and defects were evaluated in the same manner as in Test Example 1. The results are shown in the following table. [table 3]

As is clear from the above table, the coloring composition of the example can suppress the occurrence of color unevenness and defects even after passing through the prebaking. Further, the pattern shape is good and the pattern defect is small. On the other hand, the color unevenness and the defect of the comparative example were inferior. Further, the pattern shape is poor and the pattern is defective.

no

no

no

Claims (15)

A colored composition comprising a dye multimer and a curable compound, wherein the dye multimer comprises a dye structure having a structure in which an azo group or an aromatic ring group is bonded to two or more A hetero atom and a cationic heterocyclic ring in which one or more of the hetero atoms is a nitrogen atom. The coloring composition according to claim 1, wherein the cationic heterocyclic ring is represented by the following formula (I); Y ^a represents a sulfur atom or -NR ^Ya -, Y ^b represents a nitrogen atom or -CR ^Yb -, and R ^a , R ^b , R ^Ya and R ^Yb each independently represent a hydrogen atom, a substituent, and an atomic group constituting a dye structure. a bonding site or a bonding site with an atomic group constituting the dye multimer, and R ^a and R ^Ya , R ^b and R ^Ya , and R ^b and R ^Yb may be bonded to each other to form a ring; Either or the ring as a whole has a monovalent positive charge. The colored composition according to claim 1 or 2, wherein the pigment structure is represented by the formula (Ia); Ht represents a cationic heterocyclic ring containing two or more hetero atoms and one or more of the hetero atoms is a nitrogen atom, L represents -N=N-, or an extended aryl group, B represents a substituent, X represents an anion, Ht, B and At least one of X has a bonding site with an atomic group constituting the dye multimer. The colored composition according to Item 1 or 2, wherein the dye multimer has a dye structure represented by the formula (I-1); In the formula (I-1), R ¹ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ and R ⁹ to R ^{1 2} each independently represent a hydrogen atom or a substituent. a group, Y ¹ represents a sulfur atom or -NR ^{Y 1} -, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ to R ² , R ⁷ to R ^{1 2} , R ^Y1 and At least one of X has a bonding site with an atomic group constituting the dye multimer. The colored composition according to claim 1 or 2, wherein the dye multimer has a dye structure represented by formula (I-2); In the formula (I-2), R ^{1 01} , R ^{11 0} and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^{1 02} to R ^{1 05} , R ^{1 06} to R ^{1 09} Each independently represents a hydrogen atom or a substituent, and R ^{11 0} and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or -NR ^{Y 2} -, and R ^{Y 2} represents a hydrogen atom, an alkyl group, an aryl group or a hetero atom. The ring group, X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^{Y 2} and X has a bonding site with an atomic group constituting the dye multimer. The coloring composition according to the first or second aspect of the invention, wherein the dye multimer comprises a repeating unit represented by the following formula (A) and a repeat represented by the following formula (C) At least one of the units is formed by or represented by the following formula (D); In the formula (A), A ¹ represents a main chain of a repeating unit, L ¹ represents a single bond or a divalent linking group, and DyeI represents an azo group or an aromatic ring group bonded to contain two or more hetero atoms and a dye structure having a structure in which one or more hetero atoms are a cationic heterocyclic ring of a nitrogen atom; In the formula (C), L ³ represents a single bond or a divalent linking group, and DyeIII represents an azo group or an aromatic ring group bonded to two or more hetero atoms and one or more of the hetero atoms is a nitrogen atom. a pigment structure of a structure formed by a cationic heterocyclic ring, m represents 0 or 1; In the formula (D), L ⁴ represents a (n+k)-valent linking group, n represents an integer of 2 to 20, k represents an integer of 0 to 20, and DyeIV represents an azo group or an aromatic ring-based bond to be contained. a dye structure having a structure in which two or more hetero atoms and one or more of the hetero atoms are a cationic hetero ring of a nitrogen atom, and P represents a substituent. When n is 2 or more, a plurality of DyeIVs may be different from each other. When k is 2 or more, a plurality of Ps may be different from each other, and n+k represents an integer of 2 to 20. The colored composition according to claim 1 or 2, wherein the dye multimer has a bis(sulfonyl) quinone imine anion or a tris(sulfonyl)methyl anion. The colored composition according to Item 1 or 2 of the patent application, which further contains a pigment. The coloring composition according to the first or second aspect of the invention, wherein the curable compound contains a radically polymerizable compound, and the coloring composition further contains a photopolymerization initiator. The colored composition according to claim 1 or 2, further comprising an alkali-soluble resin. A color filter using the coloring composition according to any one of claims 1 to 10. A pattern forming method comprising: a step of forming a colored composition layer on a support using the coloring composition according to any one of claims 1 to 10; and a photolithography method Or a step of patterning the colored composition layer by dry etching. A solid-state image sensor having a color filter as described in claim 11 of the patent application. An image display device having the color filter of claim 11 of the patent application. a pigment multimer having a dye structure represented by the following formula (I-1) or formula (I-2); In the formula (I-1), R ¹ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² , R ⁷ and R ⁹ to R ^{1 2} each independently represent a hydrogen atom or a substituent. a group, Y ¹ represents a sulfur atom or -NR ^{Y 1} -, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, X represents an anion, R ¹ to R ² , R ⁷ to R ^{1 2} , R ^Y1 and At least one of X has a bonding site with an atomic group constituting the dye multimer; In the formula (I-2), R ^{1 01} , R ^{11 0} and R ¹¹¹ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^{1 02} to R ^{1 05} , R ^{1 06} to R ^{1 09} Each independently represents a hydrogen atom or a substituent, and R ^{11 0} and R ¹¹¹ may be bonded to form a ring, Y ² represents a sulfur atom or -NR ^{Y 2} -, and R ^{Y 2} represents a hydrogen atom, an alkyl group, an aryl group or a hetero atom. The ring group, X represents an anion, and at least one of R ¹⁰¹ to R ¹⁰⁹ , R ^{Y 2} and X has a bonding site with an atomic group constituting the dye multimer.