JP6691134B2 - Curable composition, optical filter, color filter, pattern forming method, solid-state image sensor and image display device - Google Patents

Description

  The present invention relates to curable compositions. Further, the present invention relates to a color filter, a pattern forming method, a solid-state image sensor, an image display device, and a dye multimer using a curable composition.

  2. Description of the Related Art In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements.

For example, Patent Document 1 describes manufacturing a color filter using a curable composition containing a xanthene dye, a binder, and a polymerizable compound. In paragraph 0129 of the document, the following compound is described as an example of a xanthene dye.

  Further, Patent Document 2 describes that a color filter is manufactured using a curable composition containing a dye chemically bonded to a polymer chain.

JP, 2014-219663, A JP, 2000-162429, A

  However, a cured film using a curable composition containing a dye as disclosed in Patent Document 1 or Patent Document 2 tends to cause color transfer to an adjacent cured film. Furthermore, the chemical resistance was not sufficient.

  Therefore, an object of the present invention is to provide a curable composition, an optical filter, a color filter, a pattern forming method, a solid-state image sensor, and an image display device capable of producing a cured film having excellent color transfer property and chemical resistance. Especially.

As a result of diligent studies, the present inventors have found that a curability containing a compound A having two or more dye structures and one or more mercapto groups and a curable compound having two or more curable groups. It was found that the above objects can be achieved by using the composition, and the present invention has been completed. The present invention provides the following.
<1> A curable composition comprising a compound A having two or more dye structures and one or more mercapto groups, and a curable compound having two or more curable groups.
<2> The curable composition according to <1>, wherein the curable group of the curable compound is at least one selected from a group having an ethylenically unsaturated bond and an epoxy group.
<3> The curable composition according to <1>, wherein the curable compound contains a curable compound having two or more epoxy groups.
<4> The dye structure of the compound A is a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyanine dye structure, a squarylium dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a subphthalocyanine dye structure, an azo dye structure, The curable composition according to any one of <1> to <3>, which is at least one kind selected from a thiazole dye structure, a pyrazolotriazole dye structure, and a dipyrromethene dye structure.
<5> Compound A contains at least one of a repeating unit represented by the following formula (A), a repeating unit represented by the formula (B) and a repeating unit represented by the formula (C), and mercapto A compound having a group,
Alternatively, the curable composition according to any one of <1> to <4>, which is a compound represented by the formula (D);
In formula (A), X ¹ represents a main chain of repeating units, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye structure;
In formula (B), X ² represents a main chain of a repeating unit, L ² represents a single bond or a divalent linking group, D ² is a dye structure having a group capable of forming an ionic bond or a coordinate bond with Y ^2. And Y ² represents a group capable of forming an ionic bond or a coordinate bond with D ² .
In formula (C), L ³ represents a single bond or a divalent linking group, D ³ represents a dye structure, and m represents 0 or 1.
In formula (D), L ⁴ represents a (n + k + q) -valent linking group, L ^{11 to} L ¹³ each independently represent a single bond or a divalent linking group, D ⁴ represents a dye structure, and SH Represents a mercapto group, P ¹ represents a substituent other than a mercapto group; n represents an integer of 2 to 15, k represents an integer of 0 to 13, q represents an integer of 0 to 12; D ⁴ When the dye structure represented by does not have a mercapto group, n represents 2 to 15, k represents 1 to 13, q represents 0 to 12, n + k + q represents 3 to 15; and D ⁴ represents. When the dye structure has a mercapto group, n represents 2 to 15, k represents 0 to 13, q represents 0 to 12, and n + k + q represents 2 to 15.
<6> The compound A is a curable composition according to <5>, which contains a repeating unit represented by the formula (E);
In formula (E), X ⁵ represents a main chain of a repeating unit, L ⁵ represents a single bond or a divalent linking group, and SH represents a mercapto group.
<7> Compound A is a compound represented by formula (D), n represents 2 to 15, k represents 1 to 13, q represents 0 to 12, and n + k + q represents 3 to 15. The curable composition according to <5>.
<8> The curable composition according to any one of <1> to <7> for forming a colored layer of a color filter.
<9> An optical filter using the curable composition according to any one of <1> to <8>.
<10> A color filter using the curable composition according to any one of <1> to <8>.
<11> A step of forming a curable composition layer on a support using the curable composition according to any one of <1> to <8>, and a curable composition by a photolithography method or a dry etching method. And a step of forming a pattern on the object layer.
<12> A solid-state image sensor having the optical filter according to <9>.
<13> An image display device having the optical filter according to <9>.

  According to the present invention, it is possible to provide a curable composition, an optical filter, a color filter, a pattern forming method, a solid-state imaging device, and an image display device capable of producing a cured film having excellent color transfer and chemical resistance. It became possible.

Hereinafter, the content of the present invention will be described in detail.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, light means actinic rays or radiation. The “actinic ray” or “radiation” means, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like.
Unless otherwise specified, the term "exposure" used in the present specification refers to not only exposure to deep ultraviolet rays typified by mercury lamps and excimer lasers, X-rays and EUV light, but also drawing with particle beams such as electron beams and ion beams. Include in exposure.
In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the present specification, the total solid content refers to the total mass of the components of the curable composition excluding the solvent.
In the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, "(meth) acrylic" represents both acrylic and methacrylic, or "(meth ) "Allyl" represents both allyl and methallyl or either, and "(meth) acryloyl" represents both acryloyl and methacryloyl.
In the present specification, the term “process” is included in this term as long as the intended action of the process is achieved not only as an independent process but also when it cannot be clearly distinguished from other processes. .
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values by gel permeation chromatography (GPC) measurement.

<Curable composition>
The curable composition of the present invention contains a compound A having two or more dye structures and one or more mercapto groups, and a curable compound having two or more curable groups.
By using the curable composition of the present invention, a cured film having excellent color transfer properties and chemical resistance can be produced. It is speculated that the mechanism for obtaining such an effect is as follows. Since the compound A has a mercapto group, it is speculated that the curable group of the curable compound and the mercapto group of the compound A react with each other and the compound A is easily fixed in the film. In addition, since compound A has two or more dye structures, it is presumed that compound A is easily incorporated into the film, and compound A is less likely to move in the film. Therefore, it is presumed that a cured film excellent in color transfer property can be obtained. In addition, the mercapto group of the compound A can promote the reaction between the curable groups of the curable compound to produce a sufficiently cured cured film. Therefore, it is presumed that the compound A or the like is less likely to be eluted from the cured film even when immersed in a chemical such as a solvent, and a cured film excellent in chemical resistance can be obtained.
Hereinafter, the curable composition of the present invention will be described in detail.

<< Compound A >>
The curable composition of the present invention contains a compound A having two or more dye structures and one or more mercapto groups. The compound A may be either a pigment or a dye, but is preferably a dye. Even if the compound A is used as a dye, the color transfer can be suppressed, so that the effect of the present invention is particularly remarkable. In the present invention, the dye refers to a dye compound that is soluble in water or an organic solvent. For example, a pigment compound that dissolves in 0.1 g or more with respect to 100 g of cyclohexanone or propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. is preferable.

The compound A has one or more mercapto groups in one molecule, and preferably has two or more mercapto groups. The upper limit is more preferably 10 or less.
The mercapto group may be bonded to the dye structure A. That is, a mercapto group may be bonded as a substituent of the dye skeleton.
Further, the mercapto group may be bonded to an atomic group other than the dye structure, which constitutes the compound A. For example, when compound A has a structure in which two or more dye structures are bonded to a divalent or higher valent linking group, a mercapto group may be bonded to the linking group that bonds the dye structures together. . Further, in the case where the compound A contains at least one selected from a repeating unit having a dye structure in its side chain and a repeating unit having a dye structure in its main chain, a repeating unit having a dye structure is used. A mercapto group may be bonded to another repeating unit.
In the present invention, the mercapto group is preferably bonded to an atomic group other than the dye structure constituting Compound A.

  The compound A has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The dye structures contained in one molecule may be the same dye structure or different dye structures. In the present invention, different dye structures include not only dye structures having different dye skeletons but also dye structures having the same dye skeleton and different kinds of substituents bonded to the dye skeleton. And In the present invention, the dye structure means a structure derived from a dye compound. For example, the structure which removed one or more arbitrary atoms which a dye compound has is mentioned.

  The dye structure may be a structure derived from a dye compound having absorption in the visible region (preferably in the wavelength range of 400 to 700 nm, more preferably in the range of 400 to 650 nm), and a dye having absorption in the infrared region. The structure may be derived from a compound (preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm). A structure derived from a dye compound having absorption in the visible region is preferable.

  Examples of the dye structure include triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, pyrazolotriazole dye. Structure, dipyrromethene dye structure, isoindoline dye structure, thiazole dye structure, benzimidazolone dye structure, perinone dye structure, pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, diimmonium dye structure, naphthalocyanine dye structure, rylene dye structure , Dibenzofuranone dye structure, merocyanine dye structure, croconium dye structure, oxonol dye structure and the like. Among them, triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, thiazole dye structure, pyrazolotriazole dye structure At least one selected from the structure and the dipyrromethene dye structure is preferable. Further, a dye structure derived from the thiazole compound described in JP 2012-158649 A, a dye structure derived from the azo compound described in JP 2011-18449 A, an azo compound described in JP 2011-145540 A. A dye structure derived from is also preferably used. The dye structure preferably used in the present invention will be specifically described below.

(Triarylmethane dye structure)
A preferred embodiment of the dye structure has a partial structure derived from a triarylmethane dye (triarylmethane compound). Examples of the triarylmethane dye include compounds represented by the following formula (TP). The triarylmethane compound is a generic term for compounds having a dye moiety containing a triarylmethane skeleton in the molecule.

Expression (TP)

Wherein (TP), Rtp ¹ ~Rtp ⁴ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ^7, and Rtp ⁸ represent a substituent. a, b, and c represent the integer of 0-4. When a, b and c are 2 or more, Rtp ^6's , Rtp ^7's and Rtp ^8's may be linked to each other to form a ring. X represents an anion. If X is not present, including at least one anion of Rtp ¹ ~Rtp ^7.

In the formula (TP), it is preferably bound to the other site of the compound A via any one of Rtp ^{1 to} Rtp ¹⁰ , and more preferably the other site of the compound A is bound via Rtp ⁵ . Is bound to the site.

As Rtp ¹ ~Rtp ^6, preferably a hydrogen atom, a linear or branched alkyl group and a phenyl group having 1 to 5 carbon atoms preferred. Rtp ⁵ is preferably a hydrogen atom or NRtp ⁹ Rtp ¹⁰ , and particularly preferably NRtp ⁹ Rtp ¹⁰ . Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. Examples of the substituent represented by Rtp ⁶ , Rtp ^7, and Rtp ⁸ include the substituent group A described later. Particularly, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfo group is preferable, and a linear chain having 1 to 5 carbon atoms. Alternatively, a branched alkyl group, an alkenyl group having 1 to 5 carbon atoms, a phenyl group or a carboxyl group is more preferable. Particularly, Rtp ⁶ and Rtp ⁸ are preferably an alkyl group having 1 to 5 carbon atoms, and Rtp ⁷ is preferably an alkenyl group (particularly preferably a phenyl group in which two adjacent alkenyl groups are linked), a phenyl group or a carboxyl group. .

In formula (TP), X represents a counter anion. If X is not present, including at least one anion of Rtp ¹ ~Rtp ^7. At least one of Rtp ¹ ~Rtp ⁷ but preferably includes an anion. According to this aspect, it is easy to manufacture a film having better chemical resistance.

  The counter anion is not particularly limited. The counter anion may be an organic anion or an inorganic anion, and an organic anion is preferable. Examples of the counter anion include fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, and non-nucleophilic anion. From the viewpoint of heat resistance, a non-nucleophilic anion is preferred. Examples of the counter anion include known non-nucleophilic anions described in paragraph No. 0075 of JP2007-310315A, the contents of which are incorporated herein. Here, the non-nucleophilic property means a property that the dye is not nucleophilically attacked by heating.

  The counter anion is preferably an imide anion (for example, bis (sulfonyl) imide anion), tris (sulfonyl) methyl anion, and an anion having a boron atom, more preferably bis (sulfonyl) imide anion and tris (sulfonyl) methyl anion. The sulfonyl) imide anion is more preferred.

The imide anion preferably has a structure represented by the following general formula (AN-1).
In 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 combine with 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 preferably a fluorine atom or a C 1-10 alkyl group having a fluorine atom or a C 6-10 aryl group, and more preferably a C 1-10 perfluoroalkyl group. , A perfluoroalkyl group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.
Y ¹ and Y ^2, at least one of -SO ₂ - preferably represents an, both -SO ₂ - and more preferably represents.

As the tris (sulfonyl) methyl anion, a structure represented by general formula (AN-2) shown below is preferable.
In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a halogen atom or an alkyl group. X ^3, X ⁴ and the carbon number of the alkyl group X ⁵ represents the 1 to 10 preferably 1 to 4 is more preferred. The alkyl group may be an unsubstituted alkyl group or may have a substituent. As the substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
X ³ , X ⁴ and X ⁵ are each independently 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 a C 1-4 perfluoroalkyl group. It is more preferable, and a trifluoromethyl group is particularly preferable.

  Examples of the anion having a boron atom include tetrafluoroborate anion, tetraphenylborate anion, and tetraperfluorophenylborate anion.

  The counter anion may further have a crosslinkable group. As the crosslinkable group, a group having an ethylenically unsaturated bond (for example, a vinyl group, an allyl group, a styryl group, a (meth) acryloyl group), a group having a cyclic ether structure such as an epoxy group or an oxetanyl group, and methylol Groups and the like.

  The molecular weight of the counter anion is preferably 100 to 1,000, more preferably 200 to 500. Specific examples of the counter anion are shown below, but the present invention is not limited thereto.

  In formula (TP), a, b, or c each independently represents an integer of 0 to 4. Particularly, a and c are preferably 0 or 1, and more preferably 0. b is preferably an integer of 0 to 2, more preferably 0 or 2.

In formula (TP), when at least one of Rtp ^{1 to} Rtp ⁷ contains an anion, the anion includes —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, and tris (sulfonyl) methide anion. And tetraarylborate anions are preferable, bis (sulfonyl) imide anions, tris (sulfonyl) methide anions and tetraarylborate anions are more preferable, and bis (sulfonyl) imide anions and tris (sulfonyl) methide anions are more preferable. Specifically, at least one Rtp ¹ ~Rtp ^7, include structure substituted in equation (P).
Formula (P)
In formula (P), L represents a single bond or a divalent linking group, and X ¹ represents an anion.

The divalent linking group represented by L is preferably —NR ¹⁰ —, —O—, —SO ₂ —, an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a combination thereof. In particular, a group consisting of a combination of —NR ¹⁰ — and —SO ₂ — and an alkylene group containing a fluorine atom, a group consisting of a combination of —O— and an arylene group containing a fluorine atom, or —NR ¹⁰ — and — A group consisting of a combination of SO ₂ — and an alkylene group containing a fluorine atom is preferable.
In —NR ¹⁰ —, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom.
1-10 are preferable, as for carbon number of the alkylene group containing a fluorine atom, 1-6 are more preferable, and 1-3 are further more preferable. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include difluoromethylene group, tetrafluoroethylene group, hexafluoropropylene group and the like.
6-20 are preferable, as for carbon number of the arylene group containing a fluorine atom, 6-14 are more preferable, and 6-10 are more preferable. Specific examples of the arylene group containing a fluorine atom include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, a hexafluoro-2-naphthylene group and the like.

In formula (P), X ¹ represents an anion, and is one selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion. Is more preferable, one selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion and a tetraarylborate anion is more preferable, and a bis (sulfonyl) imide anion or a tris (sulfonyl) methide anion is further preferable.

If Rtp ¹ ~Rtp ⁷ at least one of which contains an anion, at least one of Rtp ¹ ~Rtp ^7, substituted structure formula (P-1) is also preferred.
Formula (P-1)
In formula (P-1), L ¹ represents a single bond or a divalent linking group, and preferably a single bond. Examples of the divalent linking group represented by L ¹ include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —S—, or a group formed of a combination thereof. L ² is, -SO ₂ - represents a or -CO-. G represents a carbon atom or a nitrogen atom. n1 represents 2 when G is a carbon atom and 1 when G is a nitrogen atom. R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two R ⁶ may be the same or different. 1-10 are preferable, as for carbon number of the alkyl group containing the fluorine atom which R < ⁶ > represents, 1-6 are more preferable, and 1-3 are more preferable. R ⁶ carbon atoms in the aryl group containing represents fluorine atom, preferably 6 to 20, more preferably 6 to 14, 6 to 10 is more preferable.

(Xanthene dye structure)
A preferred embodiment of the dye structure has a partial structure derived from a xanthene dye (xanthene compound). Examples of the xanthene dye include compounds represented by the following formula (J).

(Formula J)

In formula (J), R ⁸¹ , R ⁸² , R ^83, and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m Represents an integer of 0 to 5. X represents a counter anion. When X is absent, at least one of R ^{81 to} R ⁸⁵ contains an anion.

In formula (J), it is preferably bound to the other site of the compound A via any one of R ^{81 to} R ⁸⁵ , and more preferably the other site of the compound A via R ^85. Is combined with.

Examples of the substituent that R ^{81 to} R ⁸⁵ in the formula (J) can have include the substituent group A described later. R ⁸¹ and R ⁸² in the formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to each other to form a 5-, 6- or 7-membered saturated ring. Or a 5-, 6- or 7-membered unsaturated ring may be formed. Examples of the ring to be formed include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, Examples thereof include a pyrazine ring and a pyridazine ring, and a benzene ring and a pyridine ring are preferable.
When the ring formed is a further substitutable group, it may be substituted with the substituents described for R ^{81 to} R ⁸⁵ , and when it is substituted with two or more substituents, The substituents may be the same or different.

In formula (J), R ⁸² and R ⁸³ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R ⁸¹ and R ⁸⁴ are preferably a substituted or unsubstituted alkyl group or a phenyl group. Examples of the substituent include the substituent group A described later. Further, R ⁸⁵ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group or an amide group, and a sulfo group, a sulfonamide group, a carboxyl group, More preferably, it is an amide group. R ⁸⁵ is preferably bonded to the adjacent portion of the carbon linked to the xanthene ring. The substituent which the phenyl group of R ⁸¹ and R ⁸⁴ has is particularly preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group or a carboxyl group.

In formula (J), X represents a counter anion. Examples of the counter anion include the counter anion described in the above formula (TP). When X is absent, at least one of R ^{81 to} R ⁸⁵ contains an anion. At least one of R ^{81 to} R ⁸⁵ preferably contains an anion. According to this aspect, it is easy to manufacture a film having better chemical resistance.

In the formula (J), when at least one of R ^{81 to} R ⁸⁵ contains an anion, examples of the anion include the anions described in the formula (TP).

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

(Anthraquinone dye structure)
A preferred embodiment of the dye structure in the invention has a partial structure derived from an anthraquinone dye. As the anthraquinone dye (anthraquinone compound), compounds represented by the following general formulas (AQ-1) to (AQ-3) are preferable. The anthraquinone compound is a general term for compounds having a dye moiety containing an anthraquinone skeleton in the molecule.

In formula (AQ-1), A and B each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom. Xqa represents ORqa ¹ or NRqa ² Rqa ³ . Rqa ¹ ~Rqa ³ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq _{1 to} Rq ₄ represent a substituent. Substituents that Rq _{1 to} Rq ₄ can have are the same as the substituents described in the section of Substituent group A described later. Ra and Rb each independently represent a hydrogen atom, an alkyl group or an aryl group.

In general formula (AQ-2), C and D have the same meanings as A and B in general formula (AQ-1). Xqb represents ORqb ¹ or NRqb ² Rqb ³ . Rqb ¹ ~Rqb ³ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₅ to Rq ₈ represents a substituent. Rq ₅ to Rq ₈ is the general formula as defined in _{(AQ-1) Rq 1 ~Rq} 4 in. Rc has the same meaning as Ra or Rb in formula (AQ-1).

In general formula (AQ-3), E and F have the same meanings as A and B in general formula (AQ-1). Xqc represents ORqc ¹ or NRqc ² Rqc ³ . Rqc ¹ ~Rqc ³ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq _{9 to} Rq ₁₂ have the same meaning as Rq ₁ to Rq _{4 in} formula (AQ-1). Rd has the same meaning as Ra or Rb in formula (AQ-1).
As preferred ranges of the general formulas (AQ-1), (AQ-2) and (AQ-3), for example, paragraphs 0045 to 0047 of JP2013-29760A can be referred to, and the content thereof is the present. Incorporated in the description.

  As the anthraquinone dye, for example, paragraphs 0049 to 0050 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Cyanine dye structure)
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a cyanine dye (cyanine compound). As the cyanine dye, a compound (cyanine compound) represented by the following general formula (PM) is preferable. In the present invention, the cyanine compound is a generic term for compounds having a dye moiety containing a cyanine skeleton in the molecule.

Expression (PM)

  In formula (PM), ring Z1 and ring Z2 each independently represent a heterocycle which may have a substituent. l represents an integer of 0 or more and 3 or less. X represents an anion. Examples of the substituent include the substituent group A described later. Examples of the anion include the counter anion described in the above formula (TP). As the preferable range of the formula (PM), for example, paragraphs 0077 to 0084 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Squarylium dye structure)
A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a squarylium dye (squarylium compound). As the squarylium dye, a compound represented by the following general formula (K) (squarylium compound) is preferable. In the present invention, the squarylium compound is a generic term for compounds having a dye moiety containing a squarylium skeleton in the molecule.

Expression (K)

  In formula (K), A and B each independently represent an aryl group or a heterocyclic group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples thereof include pyrroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazoyl and the like. . As a preferable range of the formula (K), for example, paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. As specific examples of the squarylium dye, for example, paragraph 0105 of JP 2013-29760 A can be referred to.

(Phthalocyanine dye)
A preferred embodiment of the dye structure in the present invention is one having a partial structure derived from a phthalocyanine dye (phthalocyanine compound). As the phthalocyanine dye, those having a partial structure derived from a compound (phthalocyanine compound) represented by the following formula (PC) are preferable. In the present invention, the phthalocyanine compound is a generic term for compounds having a dye moiety containing a phthalocyanine skeleton in the molecule.

Expression (PC)

In formula (PC), M represents a metal. R ^{1 to} R ¹⁶ represent a hydrogen atom, a halogen atom, an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group and a heterocyclic thio group. However, at least one of R ^{1 to} R ¹⁶ is an alkylalkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group and a heterocyclic thio group.

Examples of the metals represented by M include metal atoms such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, AlCl, InCl, FeCl. , Metal chlorides such as TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) _2, but especially Cu, VO, Zn. Are preferable, and Cu is more preferable.

When R ^{1 to} R ¹⁶ represent a halogen atom, the halogen atom is preferably a chlorine atom or a fluorine atom.
When R ^{1 to} R ¹⁶ represent an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 12. The alkyl chain portion of the alkoxy group is preferably a straight chain or a branched chain. The alkoxy group may have a substituent, and the substituent is preferably an ethylenically unsaturated bond group, more preferably a vinyl group.
When R ^{1 to} R ¹⁶ represent an arylalkoxy group, the arylalkoxy group preferably has 7 to 18 carbon atoms, and more preferably has 7 to 12 carbon atoms.
When R ^{1 to} R ¹⁶ represent a heterocyclic alkoxy group, the heterocyclic ring may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of hetero atoms constituting the hetero ring is preferably 1 to 3. The hetero atom is preferably a nitrogen atom.
When R ^{1 to} R ¹⁶ represent an alkylthio group, the alkylthio group preferably has 1 to 18 carbon atoms, more preferably has 1 to 15 carbon atoms, and further preferably has 1 to 12 carbon atoms.
When R ^{1 to} R ¹⁶ represent an arylthio group, the arylthio group preferably has 6 to 18 carbon atoms, and more preferably has 6 to 12 carbon atoms.
When R ^{1 to} R ¹⁶ represent a heterocyclic thio group, the heterocyclic ring has the same meaning as the heterocyclic ring described above for the heterocyclic alkoxy group.

  As a preferable range of the formula (PC), for example, paragraphs 0118 to 0124 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. As specific examples of the phthalocyanine dye, for example, paragraph 0123 of JP2013-29760A can be referred to.

(Subphthalocyanine dye)
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a subphthalocyanine dye (subphthalocyanine compound). As the subphthalocyanine dye, a compound represented by the following general formula (SP) (subphthalocyanine compound) is preferable. In the present invention, the subphthalocyanine compound is a general term for compounds having a dye moiety containing a subphthalocyanine skeleton in the molecule.

In formula (SP), Z ^{1 to} Z ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group or a thioether group. X represents an anion. As a preferable range of the general formula (SP), for example, paragraphs 0128 to 0133 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
For specific examples of the subphthalocyanine dye, the description in paragraph 0132 of JP 2013-29760 A can be referred to.

(Quinophthalone dye)
A preferred embodiment of the dye structure in the invention has a partial structure derived from a quinophthalone dye (quinophthalone compound). As the quinophthalone dye, a compound (quinophthalone compound) represented by the following formula (QP) is preferable. In the present invention, the quinophthalone compound is a generic term for compounds having a dye moiety containing a quinophthalone skeleton in the molecule.

Formula (QP)

In formula (QP), Rqp _{1 to} Rqp ₆ each independently represent a hydrogen atom or a substituent. Rqp ₁ If ~Rqp least two ₆ but in the adjacent position may be bonded to each other to form a ring, may have the ring formed further substituents. As a preferable range of the formula (QP), for example, paragraphs 0110 to 0114 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Azo dye structure)
A preferred embodiment of the dye structure in the invention has a partial structure derived from an azo dye (azo compound). In the present invention, the azo compound is a generic term for compounds having a dye moiety containing an N = N group in the molecule. As the azo dye, a known azo dye (eg, substituted azobenzene) can be appropriately selected and applied. For example, as the azo dye, the description in paragraphs 0084 to 0134 of JP2013-41097A and the descriptions in paragraphs 0029 to 0136 of JP2011-162760A can be referred to, and the contents thereof are incorporated in the present specification. .

  The azo dye structure is also preferably a partial structure derived from the dye compound represented by the formula (I-1).

In 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 ¹² are each independently. , A hydrogen atom or a substituent, Y ¹ represents a sulfur atom or —NR ^Y1 —, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and X represents an anion.

  Examples of the substituent include the groups described in Substituent group A described later. Examples of the anion include the anions described in the above formula (TP). For details of the dye compound represented by the formula (I-1), the descriptions in paragraphs 0010 to 0025 of JP 2011-184493 A and paragraphs 0009 to 0033 of JP 2011-145540 A can be referred to, and the contents thereof can be referred to. Are incorporated herein.

(Thiazole dye structure)
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a thiazole dye (thiazole compound). In the present invention, the thiazole compound is a compound having a thiazole ring. The thiazole dye is preferably a compound represented by the formula (I-2).

In 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, and R ^{102 to} R ¹⁰⁵ and R ^{106 to} R ¹⁰⁹ are each Each independently represents a hydrogen atom or a substituent, R ¹¹⁰ and R ¹¹¹ may combine to form a ring, Y ² represents a sulfur atom or —NR ^{Y 2} —, and R ^Y2 represents a hydrogen atom. , An alkyl group, an aryl group or a heterocyclic group, and X represents an anion.

  Examples of the substituent include the groups described in Substituent group A described later. Examples of the anion include the anions described in the above formula (TP). For details of the dye compound represented by the formula (I-2), the description in paragraphs 0008 to 0018 of JP 2012-158649 A can be referred to, and the contents thereof are incorporated in the present specification.

(Pyrazolotriazole dye structure)
A preferred embodiment of the dye structure in the present invention has a partial structure derived from a pyrazolotriazole dye (pyrazolotriazole compound). In the present invention, the pyrazolotriazole compound is a compound having a pyrazolotriazole ring. The pyrazolotriazole dye is preferably a compound represented by the formula (PA).

Formula (PA)
In formula (PA), R ^{1 to} R ⁵ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent group A described later.

  The pyrazolotriazole dye is particularly preferably a compound represented by the formula (PA-1).

R ⁴⁰¹ and R ⁴⁰² each independently represent SO ₂ R ⁴⁰³ or COR ⁴⁰³ ; R ⁴⁰³ represents an alkyl group, an aryl group or a heteroaryl group.

  Details of the pyrazolotriazole dye can be referred to the descriptions in paragraphs 0022 to 0044 of JP-A-2014-025010, the contents of which are incorporated herein.

(Dipyrromethene dye structure)
One of the embodiments of the dye structure according to the present invention has a partial structure derived from a dipyrromethene dye. The dipyrromethene dye is preferably a dipyrromethene compound or a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. For example, the dipyrromethene dye represented by the formula (I) is preferable.
Formula (I)
In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ is a hydrogen atom, a halogen atom, or an alkyl group. Represents an aryl group or a heterocyclic group. Examples of these substituents include the substituent group A described later.

The metal or metal compound forming the dipyrromethene metal complex compound will be described. The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valuable metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl, SiCl ₂ , Also included are metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ . Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex. , Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V═O) is preferable. Most preferred. Of these, Zn is particularly preferable.

  Details of the dipyrromethene dye can be referred to the descriptions of paragraphs 0045 to 0095 of JP-A-2014-132348, and the descriptions of paragraphs 0033 to 0136 of JP-A-2011-95732, the contents of which are incorporated herein. Be done.

  In the above dye structure, a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A.

(Substituent group A)
As the substituent, 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, an aryloxy group, a silyloxy group, a heterocyclic oxy group. , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl or aryl sulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, a Group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and a silyl group. The details will be described below.
Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom);
Alkyl group (straight, branched or cyclic substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl. , 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cyclohexyl and cyclopentyl. The cyclic alkyl group is a polycycloalkyl group, for example, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl). , And bicyclo [2,2,2] octane-3-yl) and tricycloalkyl groups. The cyclic alkyl group is preferably a monocyclic cycloalkyl group or a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferable);
Alkenyl group (a linear, branched or cyclic, substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, and examples thereof include vinyl, allyl, prenyl, geranyl, oleyl and 2-cyclopentene-1-. Examples of the cyclic alkenyl group include a polycycloalkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, , Bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl) and tricycloalkenyl groups are also preferred. , A monocyclic cycloalkenyl group is particularly preferable);
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group);
An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, para-tolyl, naphthyl, meta-chlorophenyl, ortho-hexadecanoylaminophenyl);
Heterocyclic groups (5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed ring heterocyclic groups are preferred, and the ring-constituting atoms are carbon atoms, nitrogen atoms, and oxygen. A heterocyclic group having at least one heteroatom of an atom or a sulfur atom is more preferable, and it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms (heteroaryl group).
Cyano group;
Hydroxyl group;
Nitro group;
Carboxyl group (hydrogen atom may be dissociated (ie, carbonate group)), salt state (metal salt (eg, sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, etc.), alkyl ammonium Salts (eg, ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, stearylamine, etc., quaternary alkylammonium salts such as palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salts, etc.) May be);
An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy);
Aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy);
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, tert-butyldimethylsilyloxy);
Heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, the heterocyclic part is preferably the heterocyclic part described in the above-mentioned heterocyclic group, for example, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy);
Acyloxy group (preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, Stearoyloxy, benzoyloxy, para-methoxyphenylcarbonyloxy);
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-dioxy). -N-octylaminocarbonyloxy, Nn-octylcarbamoyloxy);
An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy);
An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, para-methoxyphenoxycarbonyloxy, para-n-hexadecyloxyphenoxycarbonyloxy). );
Amino group (including an alkylamino group, an arylamino group and a heteroarylamino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 6 to 30 carbon atoms An arylamino group and a heteroarylamino group having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazine-2- Ilamino);
Acylamino group (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, formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino);
Aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) ;
Alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N- Methyl-methoxycarbonylamino);
Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, para-chlorophenoxycarbonylamino, meta-n-octyloxyphenoxycarbonylamino) ;
Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N-n-octylaminosulfonyl) amino);
Alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino, butyl Sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, para-methylphenylsulfonylamino);
Mercapto group;
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio);
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, para-chlorophenylthio, meta-methoxyphenylthio);
Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, the heterocyclic part is preferably the heterocyclic part described in the above-mentioned heterocyclic group, for example, 2-benzothiazoli Ruthio, 1-phenyltetrazol-5-ylthio);
Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl);
Sulfo group (hydrogen atom may be dissociated (ie, sulfonate group)), salt state (metal salt (eg, sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, etc.), alkyl ammonium Salts (eg, ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, stearylamine, etc., quaternary alkylammonium salts such as palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salts, etc.) May be);
Alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, Para-methylphenylsulfinyl);
An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, Para-methylphenylsulfonyl);
Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and examples thereof include acetyl, pivaloyl, and 2-chloroacetyl. , Stearoyl, benzoyl, para-n-octyloxyphenylcarbonyl));
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, ortho-chlorophenoxycarbonyl, meta-nitrophenoxycarbonyl, para-tert-butylphenoxycarbonyl). ;
An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl);
Carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl)
Aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic portion is described in the above heterocyclic group) Preferred heterocyclic moiety), such as phenylazo, para-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo);
An imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N-succinimide or methylphthalimide);
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino);
A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl);
A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy);
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino);
Examples thereof include a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).
When these groups are further substitutable groups, they may have further substituents. Examples of the further substituent include the groups described in the above-mentioned substituent group A.

[Preferred Embodiment of Compound A]
In the present invention, Compound A preferably has a structure in which two or more dye structures are bonded to a divalent or higher valent linking group. The compound A preferably contains at least one repeating unit having a dye structure in its side chain and at least one repeating unit having a dye structure in its main chain.

  The compound A contains at least one of a repeating unit represented by the formula (A), a repeating unit represented by the formula (B), and a repeating unit represented by the formula (C), which will be described later. Alternatively, it is preferably represented by the formula (D) described later. That is, the compound A is a dye multimer having a repeating unit represented by the formula (A) (also referred to as a dye multimer (A)) or a dye multimer having a repeating unit represented by the formula (B) (a large amount of dye). Body (B)), a dye multimer having a repeating unit represented by formula (C) (also referred to as a dye multimer (C)), and a dye multimer represented by formula (D) (a large amount of dye) The polymer (D) is preferable, the dye multimer (A) or the dye multimer (D) is more preferable, and the dye multimer (D) is further preferable.

  The weight average molecular weight (Mw) of the compound A is preferably 2000 to 50000. The lower limit is more preferably 3,000 or more, still more preferably 6000 or more. The upper limit is more preferably 30,000 or less, further preferably 20,000 or less. By satisfying the above range, it is easy to produce a cured film having excellent color transfer properties and chemical resistance. The weight average molecular weight (Mw) of the dye multimer (A) is preferably 2000 to 30000, more preferably 6000 to 15000. The weight average molecular weight (Mw) of the dye multimer (B) is preferably 2000 to 30000, more preferably 6000 to 15000. The weight average molecular weight (Mw) of the dye multimer (C) is preferably 2000 to 50,000, more preferably 6000 to 20,000. Moreover, 2000-20000 are preferable and, as for the weight average molecular weight (Mw) of a dye multimer (D), 4000-11000 are more preferable. In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of compound A are polystyrene conversion values measured by gel permeation chromatography (GPC), and are specifically described in Examples described later. It is the value measured by the method.

(Dye 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 10% by mass or more, more preferably 20% by mass or more, of all the repeating units constituting the dye multimer (A). 30 mass% or more is more preferable, and 50 mass% or more is particularly preferable. The upper limit may be 100% by mass or less, and may be 95% by mass or less.
In formula (A), X ¹ represents the main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye structure.

In formula (A), X ¹ represents a main chain of repeating units. Examples of X ¹ include a linking group formed by a polymerization reaction, and a main chain derived from a compound having a (meth) acrylic group, a styrene group, a vinyl group or an ether group is preferable. Further, an embodiment in which the main chain has a cyclic alkylene group is also preferable. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer. As X ¹ , a linking group represented by the following (XX-1) to (XX-25) is preferable, and (XX-1), (XX-2), (XX-10) to (XX-17), It is more preferably selected from (XX-18), (XX-19), (XX-24) and (XX-25), and (XX-1), (XX-2), (XX-10) to More preferably, it is selected from (XX-17), (XX-24) and (XX-25).

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

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

The alkylene group preferably has 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, further preferably 20 or less. The lower limit is more preferably 2 or more, still more preferably 3 or more. The alkylene group may be linear, branched or cyclic. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent A group.
6-20 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent A group.
The heterocyclic linking group is preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the hetero ring linking group is preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of hetero atoms contained in the heterocyclic linking group is preferably 1 to 3. The heterocyclic linking group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent A group.

D ¹ represents a dye structure. The dye structure represented by D ¹ may have a mercapto group.

  The dye multimer (A) is (1) a method of synthesizing a dye compound having a polymerizable group by addition polymerization, (2) 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 capable of reacting with a highly reactive group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.). Known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization. Among them, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye skeleton is not decomposed. Known reaction conditions can be applied to the radical polymerization. From the viewpoint of heat resistance, the dye multimer (A) is preferably a radical polymer obtained by radical polymerization using a dye compound having an ethylenically unsaturated bond.

The dye multimer (A) preferably further has a repeating unit having a mercapto group, in addition to the repeating unit represented by the formula (A). When the dye structure represented by D ^{1 of} the above formula (A) does not have a mercapto group, the dye multimer (A) has a repeating unit having a mercapto group.

The repeating unit having a mercapto group includes a repeating unit represented by the following formula (E).
In formula (E), X ⁵ represents a main chain of a repeating unit, L ⁵ represents a single bond or a divalent linking group, and SH represents a mercapto group.

In formula (E), X ⁵ represents a main chain of repeating units. Examples of X ⁵ include a linking group formed by a polymerization reaction, and a main chain derived from a compound having a (meth) acryl group, a styrene group, a vinyl group or an ether group is preferable. Further, an embodiment in which the main chain has a cyclic alkylene group is also preferable. X ⁵ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer. Specific examples of X ⁵ include the linking groups represented by (XX-1) to (XX-25) described for X ¹ in (A) above.

L ⁵ represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O ) -, - COO -, - NR -, - CONR -, - OCO -, - SO -, - SO 2 - is and linking group formed by linking two or more of these and the like. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. The details of L ⁵ are the same as the range described for L ¹ in (A) above, and the preferable range is also the same.

As for L ⁵ , the number of atoms constituting the chain connecting X ⁵ and SH is preferably 3 or more, and more preferably 4 or more. The upper limit is not particularly limited, but can be 100 or less, for example. For example, in the following case, the number of atoms constituting the chain connecting X ⁵ and SH is 11. Incidentally, the number written together with the structural formula is the number of atoms constituting the chain connecting X ⁵ and SH.

  In the dye multimer (A), the proportion of repeating units having a mercapto group (preferably the repeating unit represented by the formula (E)) is 5% by mass or more of all repeating units constituting the dye multimer (A). It is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 90 mass% or less, more preferably 80 mass% or less.

  The dye multimer (A) may contain another repeating unit in addition to the repeating unit represented by the formula (A) and the repeating unit having a mercapto group. The other repeating unit may contain a functional group such as a curable group or an acid group. It need not contain a functional group. The dye multimer preferably has at least one selected from a repeating unit having an acid group and a repeating unit having a curable group.

Examples of the curable group include a radically polymerizable group, an epoxy group, an oxazoline group, and a methylol group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as vinyl group, (meth) allyl group and (meth) acryloyl group. The curable group is preferably a radically polymerizable group.
The proportion of the repeating unit having a curable group is preferably 0 to 50% by mass of all the repeating units constituting the dye multimer (A). The lower limit is more preferably 1% by mass or more, further preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, further preferably 30% by mass or less.

  Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Only one kind of acid group may be contained, or two or more kinds thereof may be contained. The proportion of the repeating unit having an acid group is preferably 0 to 50% by mass of all the repeating units constituting the dye multimer (A). The lower limit is more preferably 1% by mass or more, further preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, further preferably 30% by mass or less.

As the other functional group, a group formed by repeating 2 to 20 unsubstituted alkyleneoxy chains, a development promoting group such as a lactone, an acid anhydride, an amide and a cyano group, a long chain and a cyclic alkyl group, an aralkyl group and an aryl group. Examples thereof include a hydrophilicity-controlling group such as a group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, and an amino group, which can be appropriately introduced. In the group consisting of 2 to 20 unsubstituted alkyleneoxy chain repeats, the number of repeating alkyleneoxy chains is more preferably 2 to 15, and even more preferably 2 to 10. One alkyleneoxy chain, - (CH ₂₎ represented by _n O-, n represents is an integer, n represents 1 to 10, more preferably 1 to 5, is 2 or 3 further preferred.

Specific examples of other repeating units are shown below, but the present invention is not limited thereto.

(Dye multimer (B))
The dye multimer (B) contains a repeating unit represented by the formula (B). In the dye multimer (B), the proportion of the repeating unit represented by the formula (B) is preferably 10% by mass or more, more preferably 20% by mass or more, of all repeating units constituting the dye multimer (B). 30 mass% or more is more preferable, and 50 mass% or more is particularly preferable. The upper limit may be 100% by mass or less, and may be 95% by mass or less.
In formula (B), X ² represents a main chain of a repeating unit, L ² represents a single bond or a divalent linking group, D ² is a dye structure having a group capable of forming an ionic bond or a coordinate bond with Y ^2. And Y ² represents a group capable of forming an ionic bond or a coordinate bond with D ² .

X ² has the same meaning as X ¹ in formula (A), and the preferred range is also the same.
L ² represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O ) -, - COO -, - NR -, - CONR -, - OCO -, - SO -, - SO 2 - is and linking group formed by linking two or more of these and the like. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. The details of the divalent linking group are the same as those for L ^{1 in} formula (A). L ² is preferably a single bond, or an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO— and a divalent linking group in which two or more thereof are combined.

Y ² may be any group capable of forming an ionic bond or a coordinate bond with D ² . Examples thereof include anionic groups and cationic groups.

Examples of the anionic _{^{group, -SO 3 -, -COO -,}} -PO 4 -, -PO 4 H -, bis (sulfonyl) imide anion, and tris (sulfonyl) methide anion and tetraarylborate anions. The anionic group is also preferably a group represented by formula (Z-1), a group represented by formula (Z-2), or a group represented by formula (Z-3).

Formula (Z-1)
* -Y ¹¹ -A ¹
In formula (Z-1), * represents a binding site with L ² in formula (B), Y ¹¹ represents a fluorinated alkylene group, and A ¹ represents SO ₃ ^— .
1-20 are preferable, as for carbon number of the fluorinated alkylene group which Y < ¹¹ > represents, 1-10 are more preferable, and 1-6 are more preferable. Further, it is more preferably a perfluoroalkylene group.

Formula (Z-2)
^{* -Y 12 - (A 2)} n
In formula (Z-2), * represents a binding site with L ² in formula (B).
Y ¹² represents an anion composed of a boron atom, a carbon atom, a nitrogen atom, or a phosphorus atom.
When Y ¹² is a boron atom, n is 3 and A ² is a halogen atom, a cyano group, an alkyl group containing at least one of a fluorine atom and a cyano group, or at least one of a fluorine atom and a cyano group. Aryl groups that include are preferred.
When Y ¹² is a carbon atom, n is 2 and A ² is a halogen atom, a cyano group, an alkyl group containing at least one of a fluorine atom and a cyano group, an aryl containing at least one of a fluorine atom and a cyano group. A group, an alkylsulfonyl group which may contain at least one of a fluorine atom and a cyano group, or an arylsulfonyl group which may contain at least one of a fluorine atom and a cyano group is preferable. Two A ^2's may combine with each other to form a ring.
When Y ¹² is a nitrogen atom, n is 1, A ² is an alkyl group containing at least one of a fluorine atom and a cyano group, an aryl group containing at least one of a fluorine atom and a cyano group, a fluorine atom and a cyano group. An alkylsulfonyl group which may contain at least one group, or an arylsulfonyl group which may contain at least one of a fluorine atom and a cyano group are preferable.
When Y ¹² is a phosphorus atom, n is 1 or 3, A ² is an alkyl group containing at least one of a fluorine atom and a cyano group, an aryl group containing at least one of a fluorine atom and a cyano group, a fluorine atom. And an alkylsulfonyl group which may contain at least one cyano group, or an arylsulfonyl group which may contain at least one of a fluorine atom and a cyano group.
When n is 2 or more, the plurality of A ² may be the same or different.

If the formula (Z-1) and formula (Z-2) contains a fluorine atom, the proportion of fluorine atoms is preferably 5% to 80% contained in Y ² with respect to the total number of atoms constituting the Y ^2,. 10 to 70% is more preferable.

Formula (Z-3)
In formula (Z-3), * represents a binding site with L ² in formula (B).
R ^{1 to} R ⁴ are preferably each independently a cyano group or a fluorinated alkyl group.

Examples of the cationic group include a substituted or unsubstituted onium cation (eg, ammonium, pyridinium, imidazolium, phosphonium, etc.), and an ammonium cation is particularly preferable. The ammonium cation, -N (R) ₃ ⁺ and the like. R's each independently represent a hydrogen atom or an alkyl group, and at least one of R's represents an alkyl group. 1-10 are preferable and, as for carbon number of an alkyl group, 1-5 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear.

D ² represents a dye structure having a group capable of forming an ionic bond or a coordinate bond with Y ² . The Y ² an ionic bond or a coordination group that can be bonded, for example, described in Y ^2, include anionic and cationic groups. Also, if the balance of charge D ² is biased to one of the cation and anion, the cation portion or the anion portion of the D ^2, can also be combined with Y ^2. The dye structure represented by D ² may have a mercapto group.

  Specific examples of the repeating unit represented by the formula (B) include structures described in paragraph numbers 0162 to 0166 of JP-A-2014-199436.

  The dye multimer (B) may contain, in addition to the repeating unit represented by the formula (B), the repeating unit having a mercapto group described in the dye multimer (A) and other repeating units. Good. Further, it may further contain a repeating unit represented by the above formula (A) and a repeating unit represented by the below described formula (C).

(Dye 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 10% by mass or more, more preferably 20% by mass or more, of all the repeating units constituting the dye multimer (C). 30 mass% or more is more preferable, and 50 mass% or more is particularly preferable. The upper limit may be 100% by mass or less, and may be 95% by mass or less.
In formula (C), L ³ represents a single bond or a divalent linking group, D ³ represents a dye structure, and m represents 0 or 1.

As the divalent linking group represented by L ³ , an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH—, —O—, —S—, — C (= O) -, - COO -, - NR -, - CONR -, - OCO -, - SO -, - SO 2 - it is and linking group formed by linking two or more of these and the like. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The alkyl group and alkylene group preferably have 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, further preferably 20 or less. The lower limit is more preferably 2 or more, still more preferably 3 or more. The alkyl group and alkylene group may be linear, branched or cyclic.
6-20 are preferable and, as for carbon number of an aryl group and an arylene group, 6-12 are more preferable.
The heterocyclic linking group and the heterocyclic group are preferably a 5-membered ring or a 6-membered ring. The hetero ring connecting group and the hetero atom contained in the hetero ring group are preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of hetero atoms contained in the heterocyclic linking group and the heterocyclic group is preferably 1 to 3.
The alkylene group, arylene group, heterocyclic linking group, alkyl group, aryl group, and heterocyclic group may be unsubstituted or may have a substituent. Examples of the substituent include a mercapto group, a curable group, and an acid group. Examples of the curable group include radically polymerizable groups such as groups having an ethylenically unsaturated bond, epoxy groups, oxazoline groups, and methylol groups. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Further, a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, a development promoting group such as lactone, acid anhydride, amide, cyano group, long chain and cyclic alkyl group, aralkyl group, aryl group, polyalkylene. It may have a hydrophobicity-controlling group such as an oxide group, a hydroxyl group, a maleimide group or an amino group as a substituent.

L ³ is preferably an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO—, —S— and a linking group in which two or more thereof are combined.
D ³ represents a dye structure. The dye structure represented by D ³ may have a mercapto group. The dye structure represented by D ³ is preferably a structure in which one or more arbitrary atoms of the dye compound are removed.
m represents 0 or 1, and 1 is preferable.

  The dye multimer (C) can be synthesized by sequential polymerization. Sequential polymerization means polyaddition (for example, reaction between diisocyanate compound and diol, reaction between diepoxy compound and dicarboxylic acid, reaction between tetracarboxylic acid dianhydride and diol, etc.) and polycondensation (for example, dicarboxylic acid). And a diol, a reaction between a dicarboxylic acid and a diamine, and the like). Of these, it is particularly preferable to synthesize by a polyaddition reaction because the reaction conditions can be moderated and the dye structure is not decomposed. Known reaction conditions can be applied to the sequential polymerization.

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

(Dye multimer (D))
The dye multimer (D) is preferably represented by the formula (D).
In formula (D), L ⁴ represents a (n + k + q) -valent linking group, L ^{11 to} L ¹³ each independently represent a single bond or a divalent linking group, D ⁴ represents a dye structure, and SH Represents a mercapto group, P ¹ represents a substituent other than a mercapto group; n represents 2 to 15, k represents 0 to 13, q represents 0 to 12; and the dye structure represented by D ⁴ is mercapto. When it has no group, n represents 2 to 15, k represents 1 to 13, q represents 0 to 12, n + k + q represents 3 to 15; and the dye structure represented by D ⁴ is a mercapto group. When it has, n represents 2-15, k represents 0-13, q represents 0-12, and n + k + q represents 2-15. When n is 2 or more, a plurality of D ⁴ may be different from each other or may be the same. When q is 2 or more, a plurality of P ¹ may be different from each other or may be the same.

In formula (D), n is preferably 2 to 15, more preferably 2 to 14, even more preferably 2 to 8, particularly preferably 2 to 7, and further preferably 2 to 6. 1-13 are preferable, 1-10 are more preferable, 1-8 are further more preferable, 1-7 are especially preferable, and 1-6 are more preferable. 0-12 are preferable, 0-10 are more preferable, 0-8 are still more preferable, 0-7 are especially preferable, and 0-6 are more preferable. 2-15 are preferable, as for the total of n, k, and q, 3-15 are more preferable, 3-14 are more preferable, 3-8 are further more preferable, 3-7 are especially preferable, 3-6 are more preferable. .
Note that n, k, and q in one dye multimer (D) are integers, respectively, but in the present invention, the compound A is a dye multimer (n, k, and q in formula (D) having different values). It may include a plurality of D). Therefore, the average value of n, k, and q in compound A may not be an integer.

L ^{11 to} L ¹³ each independently represent a single bond or a divalent linking group. The divalent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To a group consisting of up to 20 sulfur atoms are included and may be unsubstituted or may further have a substituent. Specific examples of the divalent linking group include the following structural units or groups formed by combining two or more of the following structural units.

When L ¹¹ represents a divalent linking group, the number of atoms constituting the chain connecting D ⁴ and L ⁴ is preferably 2 or more, more preferably 3 or more. The upper limit is not particularly limited, but may be, for example, 50 or less.

When L ¹² represents a divalent linking group, the number of atoms constituting the chain connecting SH and L ⁴ is preferably 2 or more, more preferably 3 or more. The upper limit is not particularly limited, but may be, for example, 50 or less.

When L ¹³ represents a divalent linking group, the number of atoms constituting the chain connecting P ¹ and L ⁴ is preferably 2 or more, and more preferably 3 or more. The upper limit is not particularly limited, but may be, for example, 50 or less.

The (n + k + q) -valent linking group represented by L ⁴ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 Included are hydrogen atoms and groups consisting of 0 to 20 sulfur atoms. Specific examples of the (n + k + q) -valent linking group include the following structural units or a group formed by combining two or more of the following structural units (which may form a ring structure). .

Specific examples of the (n + k + q) -valent linking group are shown below. However, the present invention is not limited to these. In the structural formulas below, # is a connecting position with L ^{11 to} L ¹³ . Further, the linking group described in paragraph Nos. 0071 to 0072 of JP-A-2008-222950 and the linking group described in paragraph No. 0176 of JP-A-2013-029760 are also exemplified.

In formula (D), SH represents a mercapto group, and P ¹ represents a substituent other than the mercapto group. Examples of the substituent represented by P ¹ include an acid group and a curable group. Examples of the curable group include radically polymerizable groups such as groups having an ethylenically unsaturated bond, epoxy groups, oxazoline groups, and methylol groups. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like.
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. When q is 2 or more, q P ^{1 s} may be the same or different.
When P ¹ is a monovalent polymer chain having a repeating unit and q is 1, P ¹ has 2 to 20 (preferably 2 to 15, more preferably 2) repeating units derived from a vinyl compound. Monovalent polymer chains having 10 to 10) are preferred. When P ¹ is a monovalent polymer chain having a repeating unit and q is 2 or more, the average value of the number of q repeating units derived from the vinyl compound of P ¹ is 2 to 20 ( The number is preferably 2 to 15, more preferably 2 to 10).
For monovalent polymer chains having P ¹ repeating units, the number of repeating units of P ¹ when q is 1, the average value of the number of repeating units of q P ¹ when q is 2 or more , Nuclear magnetic resonance (NMR).

When P ¹ is a monovalent polymer chain having a repeating unit, examples of the repeating unit that constitutes P ¹ include the other repeating units described in the above-mentioned dye multimer (A). The other repeating unit preferably has at least one kind selected from the repeating unit having an acid group and the repeating unit having a curable group. When it contains a repeating unit having an acid group, the developability can be improved. When it contains a repeating unit having a curable group, solvent resistance can be further improved.
When P ¹ contains a repeating unit containing an acid group, the proportion of the repeating unit containing an acid group is preferably 10 to 80 mol% and more preferably 10 to 65 mol% with respect to the total repeating units of P ^1. .
When P ¹ contains a repeating unit having a curable group, the proportion of the repeating unit having a curable group is preferably 10 to 80 mol%, and preferably 10 to 65 mol% with respect to all repeating units of P ^1. More preferable. When P ¹ contains a repeating unit having a curable group, the color transfer property can be further improved.

In the general formula (D), D ⁴ represents a dye structure. The dye structure represented by D ⁴ may be a structure in which one or more arbitrary atoms of the dye compound are removed, and a part of the dye compound may be bonded to L ⁴ , the main chain or the side chain. It may be a polymer chain containing a repeating unit having a dye structure (a structure in which one or more arbitrary atoms of the dye compound are removed) in the chain. The polymer chain is not particularly limited as long as it contains a dye structure, but it is preferably one selected from (meth) acrylic resin, styrene resin, and (meth) acrylic / styrene resin. . The repeating unit of the polymer chain is not particularly limited, but examples thereof include the repeating unit represented by the above formula (A) and the repeating unit represented by the above formula (C). In addition, the total of repeating units having a dye structure in all repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 40 mol%. preferable.

The polymer chain may contain, in addition to the repeating unit having a dye structure, other repeating units described in the dye multimer (A). As the other repeating unit, one or more kinds selected from a repeating unit having a mercapto group, a repeating unit having an acid group and a repeating unit having a curable group are preferable.
When the polymer chain contains a repeating unit having a mercapto group, the proportion of the repeating unit having a mercapto group is, for example, preferably 2 to 50 mol, more preferably 5 to 40 mol, based on 100 mol of all repeating units of the polymer chain. preferable.
When the polymer chain contains a repeating unit having a curable group, the proportion of the repeating unit having a curable group is, for example, preferably 5 to 50 mol, and preferably 10 to 40 mol, based on 100 mol of all repeating units of the polymer chain. Is more preferable.
When the polymer chain contains a repeating unit having an acid group, the proportion of the repeating unit having an acid group is, for example, preferably 5 to 50 mol, more preferably 10 to 40 mol, based on 100 mol of all repeating units of the polymer chain. preferable.

The dye multimer represented by the above formula (D) can be synthesized by the following method.
(1) A compound having a functional group selected from a carboxyl group, a hydroxyl group, an amino group or the like introduced at the terminal, and an acid halide having a dye structure, an alkyl halide having a dye structure, or an isocyanate having a dye structure. Polymer reaction method.
(2) A method of causing a Michael addition reaction between a compound having a carbon-carbon double bond introduced at its terminal and a mercapto compound having a dye structure.
(3) A method of reacting a compound having a carbon-carbon double bond introduced at its terminal with a mercapto compound having a dye structure in the presence of a radical generator.
(4) A method of reacting a polyfunctional mercapto compound having a plurality of mercapto groups introduced at the 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 mercapto compound having a dye structure.

The dye multimer (D) preferably has a structure represented by the formula (D-1).

In formula (D-1), L ⁴ represents a (n + k + q) -valent linking group. n represents an integer of 2 to 15, k represents an integer of 0 to 13, and q represents an integer of 0 to 12. D ⁴ represents a dye structure, SH represents a mercapto group, and P ¹ represents a substituent. B ¹ .about.B ³ is independently a single bond, -O -, - S -, - CO -, - NR -, - O 2 C -, - CO 2 -, - NROC-, or, -CONR- Represents R represents a hydrogen atom, an alkyl group or an aryl group. C ^{1 to} C ³ 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 ⁴ may be different from each other or may be the same. When q is 2 or more, a plurality of P ¹ may be different from each other or may be the same. When the dye structure represented by D ⁴ does not have a mercapto group, n represents 2 to 15, k represents 1 to 13, q represents 0 to 12, and n + k + q represents 3 to 15. When the dye structure represented by D ⁴ has a mercapto group, n represents 2 to 15, k represents 0 to 13, q represents 0 to 12, and n + k + q represents 2 to 15.

Wherein ^{(D-1), D 4} , P 1, L 4, n, k, q are, D of the general formula ^{(D) 4, P 1,} L 4, n, k, has the same meaning as q, preferred The range is also the same.

In formula (D-1), B ^{1 to} B ³ are each independently a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —. NROC-, or represents -CONR-, single bond, -O -, - CO -, - O 2 C -, - CO 2 -, - NROC-, or, -CONR-, more preferably a single bond, -O -, - CO -, - O 2 C- or -CO ₂ - is more preferable.
R represents a hydrogen atom, an alkyl group or an aryl group.
1-30 are preferable and, as for carbon number of the alkyl group which R represents, 1-10 are more preferable. The alkyl group may be linear, branched or cyclic.
6-30 are preferable and, as for carbon number of the aryl group which R represents, 6-12 are more preferable.
R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

In formula (D-1), C ^{1 to} C ³ each independently represent a single bond or a divalent linking group. As the divalent linking group, an alkylene group, an arylene group and a group in which these are combined are preferable. 1-30 are preferable and, as for carbon number of an alkylene group, 1-10 are more preferable. The alkylene group may be linear, branched or cyclic. 6-30 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable.

Specific examples of compound A include the following.

The curable composition of the present invention preferably contains the compound A described above in an amount of 20 to 95% by mass based on the total solid content of the curable composition of the present invention. The lower limit is preferably 25% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less.
Further, the compound A is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, based on the total mass of the compound A and other colorants described later.
When the curable composition of the present invention contains two or more compounds A, the total amount thereof is preferably within the above range.

<< other colorants >>
The curable composition of the present invention can further use a colorant (other colorant) other than the compound A described above. The other colorant may be a dye or a pigment, or both may be used in combination. Further, the other colorant may be a dye multimer.

  Examples of the pigment include various conventionally known inorganic pigments or organic pigments. The average primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast. Further, it is preferably 5 nm or more from the viewpoint of dispersion stability. The average primary particle diameter of the pigment is more preferably 5-75 nm, further preferably 5-55 nm, particularly preferably 5-35 nm. The average primary particle diameter 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 metal oxides and metal complex salts. Specifically, black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper, titanium, Examples thereof include metal oxides such as magnesium, chromium, zinc and antimony, and complex oxides of the above metals.

The following can be mentioned as organic pigments. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175 176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184. 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279.
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80
C. I. Pigment Black 1
Further, as the green pigment, use is made of a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5. Is also possible. Specific examples include the compounds described in WO2015 / 118720.
Further, as the yellow colorant, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-54339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-26228A, and the like can be used.
Further, an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue pigment. Specific examples thereof include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph 0047 of JP2011-157478A.
These organic pigments can be used alone or in various combinations for increasing color purity.

  Examples of the dye include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-2592207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,050,950, JP-A-5-333207, JP-A-6-315183, JP-A-6-51115, JP-A-6-194828 and the like. Dyes can be used. When classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. The thiazole compound described in JP 2012-158649 A, the azo compound described in JP 2011-18449 A, and the azo compound described in JP 2011-145540 A can also be preferably used. Further, a dye multimer may be used as the dye.

  Examples of the dye multimer include compounds described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, and the like.

When the curable composition of the present invention contains another colorant, the content of the other colorant is preferably 10 to 70 mass% with respect to the total solid content of the curable 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, further preferably 25% by mass or more.
Further, in the curable composition of the present invention, the proportion of the dye in the total weight of the compound A and the other colorant is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. Is more preferable. As the proportion of the dye in the curable composition increased, the color fading property and chemical resistance of the obtained cured film tended to decrease, but according to the present invention, even if a large amount of the dye is contained. It is possible to manufacture a cured film having excellent color removal and chemical resistance.
In addition, the curable composition of the present invention may be in a mode in which other colorant is not substantially contained. In addition, substantially containing no other colorant means, for example, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, based on the total solid content of the curable composition. It is more preferable not to contain a coloring agent.

<< resin >>
The curable composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition and for the purpose of a binder. The resin mainly used to disperse a colorant such as a pigment is also referred to as a dispersant. However, such an application of the resin is an example, and the resin may be used for purposes other than such an application.

  In the curable composition of the present invention, the content of the resin is preferably 1 to 80% by mass based on the total solid content of the coloring composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

<<< dispersant >>
The curable composition of the present invention may contain a dispersant as a resin. Generally, when a pigment is included as a colorant or the like, a dispersant is used. Examples of the dispersant include a polymer dispersant and a surfactant. It can be appropriately selected depending on the substance to be dispersed. The dispersant is preferably a polymer dispersant (eg, linear polymer, terminal modified polymer, graft polymer, block polymer). The polymer dispersant is preferably a graft type polymer.

Examples of the graft type polymer include polyester dispersants. Specifically, reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc. Reaction products of polyallylamine and polyester described in JP-A-169821 and the like, macromonomers described in JP-A-10-339949, JP-2004-37986A, WO 2010/110491, etc., and a nitrogen atom. A copolymer with a monomer having a group, a graft-type polymer having a partial skeleton or a heterocycle of an organic dye described in JP 2003-238837 A, JP 2008-9426 A, JP 2008-81732 A, and the like. JP-A-2010-106268, etc., copolymers of macromonomers and acid group-containing monomers, Such amphoteric resin having a basic group and an acid group described in 2009-203462 JP thereof. As the graft polymer, for example, the following polymers are preferable.

  As the dispersant, the dispersant resin agent described in paragraphs 0256 to 0264 of JP-A-2005-71743 can also be used. The resin described for the dispersant can be used for purposes other than the dispersant. For example, it can also be used as a binder.

<<<< alkali-soluble resin >>>
The curable composition of the present invention can contain an alkali-soluble resin as a resin. By containing the alkali-soluble resin, the developability and pattern formability are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The alkali-soluble resin may be a linear organic high-molecular polymer, and at least one alkali-soluble resin in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) It can be appropriately selected from alkali-soluble resins having a promoting group.

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxystyrene-based resin, polysiloxane-based resin, acrylic resin, acrylamide-based resin, acrylic / acrylamide copolymer resin is preferable, and from the viewpoint of developability control, Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. Developable ones are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be only one kind or two or more kinds.

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

  The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain, and is a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid. Examples thereof include acid copolymers, alkali-soluble phenolic resins such as novolac type resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. As vinyl compounds, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. Further, as the other monomer, the N-substituted maleimide monomer described in JP-A-10-300922 can be used. Specific examples include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, the other monomer copolymerizable with these (meth) acrylic acid may be only 1 type, and may be 2 or more types.

  Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / A multi-component copolymer composed of (meth) acrylic acid / other monomer can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654. -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 Macromonomers / benzyl methacrylate / methacrylic acid copolymers can also be preferably used. Moreover, as a commercial item, FF-426 (made by Fujikura Kasei) etc. can also be used, for example.

  Moreover, as the alkali-soluble resin, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include (meth) allyl group and (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in its side chain is useful. Examples of the alkali-soluble resin containing a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polymerethane acrylic oligomer. Manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 ( All are manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all are manufactured by Daicel Corporation), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), ACRYCURE RD-F8 ( (Manufactured by Nippon Shokubai Co., Ltd.) and the like.

  The alkali-soluble resin is a compound represented by the following general formula (ED1) and / or a compound represented by the general formula (1) in JP 2010-168539 A (hereinafter, these compounds are referred to as “ether dimer”). It is also preferable to include a polymer obtained by polymerizing a monomer component containing

In general 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 specific examples of the ether dimer, for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. The ether dimer may be only one kind or two or more kinds.

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

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The alkyl group of R ₃ has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and the alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Specific examples of the alkali-soluble resin include the following resins. In the following formula, Ph is a phenyl group.

  For the alkali-soluble resin, the description in JP 2012-208494 A, paragraphs 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, [0685] to [0700]) can be referred to, and the contents thereof are referred to. Incorporated in the description. Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in the Examples, paragraphs 0088 to 1988 of JP2012-208474A. The binder resin described in JP-A No. 009898 and the binder resin used in the examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP2012-137531A, and the binder resin used in the Examples, JP2013-2013A. No. 024934, paragraph Nos. 0132 to 0143, the binder resin used in Examples and the binder resin used in Examples, No. 2011-242752, Paragraph Nos. 0092 to 0098 and Examples, Paragraph No. of Japanese Unexamined Patent Publication No. 2012-032770 It is also possible to use a binder resin according to 030-0072. These contents are incorporated herein.

  The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, 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 further preferably 120 mgKOH / g or less.

  The content of the alkali-soluble resin is preferably 0.1 to 20 mass% with respect to the total solid content of the curable 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 curable composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably within the above range.

<< solvent >>
The curable 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 the solubility of each component and the coatability of the curable composition are satisfied.

  Examples of the organic solvent include the followings. Examples of the esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl. Alkyl oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxy Alkyl propionates (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-eth) Methyl cypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropione Acid methyl and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvate Propyl acid, Methyl cetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl. Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, Methyle Suitable examples of the chill ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons include toluene and xylene.

  The organic solvent may be used alone or in combination of two or more. When using two or more kinds of organic solvents in combination, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid. It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

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

  The content of the solvent is preferably such that the total solid content of the curable composition is 5 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 further preferably 40% by mass or less.

<< Curable Compound >>
The curable composition of the present invention contains a curable compound having two or more curable groups. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, and a methylol group. A group having an ethylenically unsaturated bond and an epoxy group are preferable, and an epoxy group is more preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group and a (meth) acryloyl group. The curable compound has two or more curable groups, and more preferably has three or more. The lower limit may be, for example, 100 or less, 50 or less, or 20 or less.

  The curable compound includes a curable compound having two or more groups having an ethylenically unsaturated bond (hereinafter also referred to as a polymerizable compound) and a curable compound having two or more epoxy groups (hereinafter also referred to as an epoxy compound). It is preferable to contain at least 1 sort (s) chosen from these, and it is more preferable to contain an epoxy compound. Since the mercapto group contained in the compound A easily reacts with the epoxy group and particularly accelerates the curing of the epoxy compound, the use of the epoxy compound makes it easy to obtain a cured film having better color loss and chemical resistance.

  The content of the curable compound is preferably 0.1 to 50 mass% with respect to the total solid content of the curable composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, further preferably 40% by mass or less. The curable compounds may be used alone or in combination of two or more. When two or more kinds are used together, the total amount is preferably within the above range.

(Polymerizable compound)
In the present invention, the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. When the polymerizable compound is a radical photopolymerizable compound, a monomer is preferred.
The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.
The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound. Specific examples of these compounds are described in paragraph Nos. 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraphs 0254 to 0257 of JP2008-292970A. Compounds may be considered, the content of which is incorporated herein.

The polymerizable compound includes dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd., and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, SR454 commercially available from Sartomer Co., SR494, SR499) Is preferred. These oligomer types can also be used. Further, KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. Moreover, the following compounds can also be used.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group and a phosphoric acid group. Examples of commercially available products include M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

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

A compound having a caprolactone structure is also a preferable embodiment of the polymerizable compound.
The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120.

  As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth) acrylate compound is more preferable.

Specific examples of the polymerizable compound having an alkyleneoxy group include the following compounds.

  Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups, manufactured by Nippon Kayaku Co., Ltd. Examples thereof include DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, use of addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238. Is also preferable.
As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-. 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

When a polymerizable compound is used as the curable compound, the content of the polymerizable compound is preferably 0.1 to 50 mass% with respect to the total solid content of the curable composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, further preferably 40% by mass or less. The curable compounds may be used alone or in combination of two or more. When two or more kinds are used together, the total amount is preferably within the above range.
Moreover, the content of the polymerizable compound may be 10 to 100% by mass, or 30 to 100% by mass, based on the total mass of the curable compound.

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

In the present invention, the epoxy compound preferably has a structure having an aromatic ring and / or an aliphatic ring, and more preferably has a structure having an aliphatic ring. The epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group. As the linking group, an alkylene group, an arylene group, -O-, -NR '-(R' is a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. And a hydrogen atom is preferable), and a group containing at least one selected from —SO ₂ —, —CO—, —O— and —S—.
In the case of a compound having an aliphatic ring, the epoxy group is preferably a compound having a direct bond (single bond) to the aliphatic ring. In the case of a compound having an aromatic ring, a compound in which the epoxy group is bonded to the aromatic ring via a linking group is preferable. The linking group is preferably an alkylene group or a group composed of a combination of an alkylene group and -O-.
Further, as the epoxy compound, a compound having a structure in which two or more aromatic rings are linked 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 compound preferably has an epoxy equivalent (= molecular weight of epoxy compound / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, and further preferably 100 to 300 g / eq. More preferable.

  The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2,000, further less than 1,000), or a macromolecular compound (for example, a molecular weight of 1,000 or more, and in the case of a polymer, a weight average molecular weight of 1,000 or more). Any of 200-100,000 are preferable and, as for the weight average molecular weight of an epoxy compound, 500-50000 are more preferable. The upper limit of the weight average molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1500 or less.

  Epoxy compounds are compounds described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014-0889408A. Can also be used. These contents are incorporated herein. As commercially available products, for example, as bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050. , EPICLON1051, EPICLON1055 (above, manufactured by DIC Corporation), etc., and as bisphenol F type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc. As the phenol novolac type epoxy resin, jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation) ) Etc., as the cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, DIC Co., Ltd.), EOCN-1020 (above, Nippon Kayaku Co., Ltd.), and the like, as the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP. -4088S (above, manufactured by ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, Daicel Corporation), Denacol EX-212L, EX-. 214L, EX-216L, EX-321L, EX-850L (above, Nagase Chemtex Co., Ltd. product) etc. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), EPICLON HP-4700, EPICLON HP-4032D (above manufactured by DIC Corporation) and the like can be mentioned.

As the epoxy compound, a polymer containing a repeating unit having an epoxy group in its side chain can also be used. For example, the following polymers can also be used.

When an epoxy compound is used as the curable compound, the content of the epoxy compound is preferably 0.1 to 50 mass% with respect to the total solid content of the curable composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, further preferably 40% by mass or less. The epoxy compounds may be used alone or in combination of two or more. When two or more kinds are used together, the total amount is preferably within the above range.
The content of the epoxy compound is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, based on the total mass of the curable compound.
When the polymerizable compound and the epoxy compound are used in combination, the mass ratio of the polymerizable compound and the epoxy compound is preferably: polymerizable compound: epoxy compound = 100: 1 to 100: 400, and 100: 1 to 100. : 100 is more preferable.

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

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

  Further, the curing accelerator is a methylol compound (for example, a compound exemplified as a cross-linking agent in paragraph 0246 of JP-A-2015-34963), amines, phosphonium salt, amidine salt, amide compound (above, for example, Japanese Patent Laid-Open No. 2013-41165, the curing agent described in paragraph 0186, a base generator (for example, the ionic compound described in JP-A-2014-55114), and a cyanate compound (for example, JP-A-2012-150180). Paragraph 0071), alkoxysilane compound (for example, alkoxysilane compound having an epoxy group described in JP 2011-253054 A), onium salt compound (for example, Paragraph 0216 of JP 2015-34963 A). Compounds exemplified as the acid generator, JP 2009- Compounds described in JP 80 949) can also be used.

  When the curable composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9 mass% with respect to the total solid content of the curable composition, and 0.8 ˜6.4% by mass is more preferred.

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

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. And other oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like. Examples of commercially available trihalomethyltriazine-based photopolymerization initiators include TAZ-107 (manufactured by Midori Kagaku).

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole compounds, benzimidazoles. Compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, compounds selected from the group consisting of 3-aryl-substituted coumarin compounds Is preferred. The following compounds are mentioned as a triaryl imidazole compound, a benzimidazole compound, and a benzophenone compound.

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

In particular, when the curable composition of the present invention is used for producing a color filter for a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape, and therefore, curability and residue on the unexposed portion are generated. It is important to develop without. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern in a solid-state imaging device, a stepper exposure machine is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the amount of photopolymerization initiator added low. Therefore, taking these points into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator for forming a fine pattern such as a solid-state image sensor. Further, by using an oxime compound, the color transfer property can be further improved.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

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

  Examples of the oxime compound such as an oxime derivative that is preferably used as the photopolymerization initiator in the present invention include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

Examples of the oxime compound include J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 156-162. 202-232, compounds described in JP 2000-66385 A, compounds described in JP 2000-80068 A, JP 2004-534797 A, JP 2006-342166 A, and the like.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Also, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), ADEKA 9 Arcs NCs. (Manufactured by ADEKA) can also be used.

  In addition, as oxime compounds other than the above description, compounds described in JP-A-2009-511904, in which an oxime is linked to the N-position of a carbazole ring, and US Pat. No. 7,626,957, in which a hetero substituent is introduced into a benzophenone moiety, Compounds, compounds in which a nitro group is introduced into the dye moiety, compounds described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039, ketoxime compounds described in International Publication WO 2009/131189, triazine skeleton and oxime skeleton are the same. A compound described in US Pat. No. 7,556,910, which is contained in the molecule, a compound described in JP2009-221114A, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, and the like may be used. . Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) -form oxime compound, a (Z) -form oxime compound, or a mixture of the (E) -form and the (Z) -form. .

In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.
Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the above-mentioned substituent may be further substituted with another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group and an aryl group.
In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.

  In the present invention, an oxime compound having a fluorene ring can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.

  In the present invention, an oxime compound having a fluorine atom can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP2010-262028A, compounds 24, 36 to 40 described in JP-A-2014-500852, and compounds described in JP2013-164471A. C-3) etc. are mentioned. This content is incorporated herein.

  In the present invention, an oxime compound having a nitro group can be used as the photopolymerization initiator. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, and ADEKA. Acruz NCI-831 (made by ADEKA) is mentioned.

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

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

From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, 000 is particularly preferable. A known method can be used to measure the molar extinction coefficient of the compound. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used, and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L.
The photopolymerization initiators may be used in combination of two or more, if necessary.

  When the curable composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0% by mass based on the total solid content of the curable composition. It is 0.5 to 30 mass%, and more preferably 1 to 20 mass%. Within this range, better sensitivity and pattern formability can be obtained. The curable composition of the present invention may contain only one type or two or more types of photopolymerization initiators. When two or more kinds are included, the total amount is preferably within the above range.

<< Pigment derivative >>
The curable composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is replaced with an acidic group, a basic group or a phthalimidomethyl group. As the organic pigment for constituting the pigment derivative, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, slene pigments, metal complex pigments and the like. As the acidic group contained in the pigment derivative, a sulfonic acid group, a carboxylic acid group and a quaternary ammonium salt group thereof are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is particularly preferable. The basic group contained in the pigment derivative is preferably an amino group, and particularly preferably a tertiary amino group. As specific examples of the pigment derivative, the description in paragraphs 0162 to 0183 of JP 2011-252065 A can be referred to, and the contents thereof are incorporated in the present specification.

  The content of the pigment derivative in the curable composition of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total mass of the pigment. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination.

<< Surfactant >>
The curable 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 a silicone-based surfactant can be used.

  By containing a fluorosurfactant in the curable composition of the present invention, the liquid properties (particularly the fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. Can be improved. That is, when a film is formed using a coating liquid to which a curable composition containing a fluorine-containing surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is wet. The property is improved, and the coating property on the surface to be coated is improved. Therefore, it is possible to more favorably form a film having a uniform thickness with a small thickness unevenness.

  The content of fluorine in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving, and also has good solubility in the composition.

Examples of the fluorine-based surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475 and F479, F482, F554, F780, RS-72-K (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC. -101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, OMNOVA company make) etc. are mentioned. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2005-117327 can also be used. A block polymer may be used as the fluorine-containing surfactant, and specific examples thereof include the compounds described in JP 2011-89090 A.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
As the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can be used as the fluorosurfactant. Specific examples thereof include the compounds described in JP-A-2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerolpropoxylate, glycerolethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF). 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, So Sparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), etc. Also, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd., Pionin D-6112- manufactured by Takemoto Yushi Co., Ltd. W, D-6315, etc. can also be used.

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

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

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd. )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shinetsu Silicone Co., Ltd.). , BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.

As the surfactant, only one kind may be used, or two or more kinds may be combined.
The content of the surfactant is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass% with respect to the total solid content of the curable composition.

<< silane coupling agent >>
The curable composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two kinds of functional groups having different reactivities in one molecule is also preferable, and one having an amino group and an alkoxy group as a functional group is particularly preferable. Examples of such a silane coupling agent include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-. Aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ -Aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropyltrimethoxy. Silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) and the like. For details of the silane coupling agent, the description in paragraph Nos. 0155 to 0158 of JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification.

  When the curable composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20 mass% with respect to the total solid content of the curable composition, and is preferably 0. 01 to 10 mass% is more preferable, and 0.1 mass% to 5 mass% is particularly preferable. The curable composition of the present invention may contain only one type or two or more types of silane coupling agents. When two or more kinds are included, the total amount is preferably within the above range.

<< polymerization inhibitor >>
The curable composition of the present invention also preferably contains a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, ceria salt, etc.) and the like can be mentioned.
When the curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass% with respect to the total solid content of the curable composition. The curable composition of the present invention may contain only one type or two or more types of polymerization inhibitors. When two or more kinds are included, the total amount is preferably within the above range.

<< Other additives >>
The curable composition of the present invention may be mixed with various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber and an agglomeration inhibitor, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A 2004-295116, the contents of which are incorporated herein. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, the compound described in paragraph 2011-90147 0042), a thioether compound, or the like can be used. Examples of commercially available products include Adeka Stab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-) manufactured by ADEKA Corporation. 330). Two or more kinds of antioxidants may be mixed and used. The curable composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph No. 0078 of JP-A 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the same.

  The curable composition may contain a metal element depending on the raw materials used, but the content of the Group 2 element (calcium, magnesium, etc.) in the curable composition is 50 ppm or less from the viewpoint of suppressing the occurrence of defects. Is preferable, and it is preferable to control to 0.01 to 10 ppm. Further, the total amount of the inorganic metal salt in the curable composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.

<Method for preparing curable composition>
The curable composition of the present invention can be prepared by mixing the above-mentioned components. There is no particular restriction on the order of addition and the working conditions when blending. For example, all the components may be dissolved and dispersed in a solvent at the same time to prepare a composition, or if necessary, each component may be appropriately used as two or more solutions or dispersions before use (at the time of coating). ) And these may be mixed and prepared.

When preparing the curable composition, it is preferable to filter with a filter for the purpose of removing foreign matters and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight). (Including the polyolefin resin), and the like. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
A suitable pore size of the filter is about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. Within this range, it becomes possible to reliably remove fine foreign substances that hinder the preparation of a uniform composition in the subsequent step and the formation of a smooth film. Further, it is also preferable to use a fibrous filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber and the like, and specifically, SBP type series (SBP008 etc.) and TPR type series (TPR002) manufactured by Roki Techno Co., Ltd. , TPR005), and SHPX type series (SHPX003, etc.) filter cartridges can be used.

When using the filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. For the pore size here, the nominal value of the filter manufacturer can be referred to. As the commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. can do.
The second filter can be made of the same material as the first filter described above.
For example, the filtering with the first filter may be performed only with the dispersion liquid, and the second filtering may be performed after mixing the other components.

  The curable composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and adjusting the film thickness. The value of the viscosity can be appropriately selected as necessary, but for example, at 25 ° C., 0.3 mPa · s to 50 mPa · s is preferable, and 0.5 mPa · s to 20 mPa · s is more preferable. As a method for measuring the viscosity, for example, a Toki Sangyo viscometer RE85L (rotor: 1 ° 34 ′ × R24, measuring range: 0.6 to 1200 mPa · s) is used, and the temperature is adjusted to 25 ° C. Can be measured.

<Optical filters, color filters>
Next, the optical filter will be described. The optical filter of the present invention comprises the curable composition of the present invention described above. The optical filter of the present invention can be used for the purpose of transmitting or blocking light of a specific wavelength. For example, it can be used as a color filter, an infrared cut filter, an infrared transmission filter, an ultraviolet cut filter, an ultraviolet transmission filter, or the like. The optical filter of the present invention may have a pattern or may be a film having no pattern (flat film). In addition, in the present invention, the color filter is a filter that allows light in a specific wavelength range to pass through and blocks light in a specific wavelength range from among light in a wavelength range of visible light (preferably wavelength of 380 to 780 nm). means. The infrared cut filter means a filter that transmits light having a wavelength in the visible region and blocks at least a part of light having a wavelength in the infrared region. The infrared cut filter may be one that transmits all light in the visible range of wavelengths, and of the light in the visible range of wavelengths, passes light in a specific wavelength range and blocks light in a specific wavelength range. It may be one. Further, the infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the infrared region. The ultraviolet cut filter may be one that transmits all the light in the visible wavelength range, and of the light in the visible wavelength range, passes light in a specific wavelength range and blocks light in a specific wavelength range. It may be one. Further, the ultraviolet transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the ultraviolet region.

  Moreover, the color filter of the present invention comprises the curable composition of the present invention described above. The color filter of the present invention can be used for solid-state image pickup devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), and image display devices.

  When the optical filter (color filter) of the present invention is used for a liquid crystal display device, the voltage holding ratio of the liquid crystal display element provided with the optical filter (color filter) is preferably 70% or more, and 90% or more. Is more preferable. Known means for obtaining a high voltage holding ratio can be incorporated as appropriate, and typical means include the use of highly pure materials (for example, reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition. Is mentioned. The voltage holding ratio can be measured by, for example, the method described in paragraph 0243 of JP 2011-008004 A, paragraphs 0123 to 0129 of JP 2012-224847 A, or the like.

The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit may be, for example, 0.1 μm or more, and may be 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 may be, for example, 0.1 μm or more, and may be 0.2 μm or more.

<Pattern forming method>
The pattern forming method of the present invention comprises a step of forming a curable composition layer on a support using the curable composition of the present invention, and a photolithography method or a dry etching method for the curable composition layer. Forming a pattern.

The pattern formation by the photolithography method includes a step of forming a curable composition layer on a support using a curable composition, a step of exposing the curable composition layer in a pattern, and a development removal of an unexposed portion. And forming a pattern. If necessary, a step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided.
Further, pattern formation by the dry etching method includes a step of forming a curable composition layer on a support using a curable composition and curing the curable composition layer to form a cured product layer, and a photoresist layer on the cured product layer. And a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the cured product layer using the resist pattern as an etching mask to form a pattern. preferable. Hereinafter, each step will be described.

<< Step of forming curable composition layer >>
In the step of forming the curable composition layer, the curable composition is used to form the curable composition layer on the support.

As the support, for example, a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
The pattern in the present invention may be formed on the solid-state image sensor forming surface side (front surface) of the solid-state image sensor substrate or on the solid-state image sensor non-forming surface side (back surface).
If necessary, an undercoat layer may be provided on the support in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a method for applying the curable composition onto the support, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be used.

The curable composition layer formed on the support may be dried (prebaked). When forming a pattern by a low temperature process, prebaking may not be performed.
When prebaking is performed, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and further preferably 110 ° C or lower. The lower limit may be, for example, 50 ° C. or higher, and may be 80 ° C. or higher. By performing the pre-baking temperature at 150 ° C. or lower, these characteristics can be more effectively maintained, for example, when the photoelectric conversion film of the image sensor is made of an organic material.
The prebake time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed with a hot plate, an oven, or the like.

(When patterning by photolithography)
<< exposure process >>
Next, the curable composition layer is exposed in a pattern (exposure step). For example, the curable composition layer can be pattern-exposed by using an exposure device such as a stepper to expose the curable composition layer through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
As the radiation (light) that can be used at the time of exposure, ultraviolet rays such as g rays and i rays are preferably used (particularly preferably i rays). Irradiation dose (exposure dose), for example, preferably ^{0.03~2.5J / cm 2, 0.05~1.0J / cm} 2 is more preferable.
The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing in the air, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) can be selected from the range of . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.
The thickness of the cured film is preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit may be, for example, 0.1 μm or more, and may be 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 process >>
Next, the unexposed portion is developed and removed to form a pattern. The development removal of the unexposed portion can be performed using a developing solution. As a result, the curable composition layer in the unexposed portion in the exposure step is eluted into the developing solution, and only the photocured portion remains.
As the developing solution, an organic alkali developing solution that does not damage the underlying solid-state imaging device or circuit is desirable.
The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.

Examples of the alkaline agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. , Dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like. As the developing solution, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
Further, an inorganic alkali may be used in the developing solution. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.
A surfactant may be used in the developer. Examples of the surfactant include the surfactants described in the above curable composition, and nonionic surfactants are preferable.
When a developing solution containing such an alkaline aqueous solution is used, it is generally preferable to wash (rinse) with pure water after the development.

After the development, drying may be performed and then heat treatment (post-baking) may be performed. Post bake is a heat treatment after development to complete the cure of the film. When post-baking is performed, the post-baking temperature is preferably 100 to 240 ° C, for example. From the viewpoint of film curing, 200 to 230 ° C is more preferable. Further, when an organic electroluminescence (organic EL) element is used as a light emitting source or when the photoelectric conversion film of the image sensor is made of an organic material, the post-baking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower. It is preferably 100 ° C. or lower, more preferably 90 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher.
The post-baking can be carried out in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (a hot-air circulation dryer), or a high-frequency heater so that the film after development can meet the above conditions. . Further, when the pattern is formed by the low temperature process, the post bake may not be performed.

(When patterning by dry etching method)
Pattern formation by a dry etching method, a curable composition layer formed on a support is cured to form a cured product layer, and then a patterned photoresist layer is formed on the resulting cured product layer, The photoresist layer can be used as a mask for etching with an etching gas. At this time, the curable composition layer is preferably formed using a thermosetting composition, and the thermosetting composition preferably contains a compound having two or more epoxy groups as a curable compound. Further, the thermosetting composition does not need to contain a photopolymerization initiator, and preferably contains substantially no photopolymerization initiator.
Specifically, it is preferable to form a photoresist layer by applying a positive or negative radiation-sensitive composition on the cured product layer and drying the composition. In forming the photoresist layer, it is preferable to further perform a prebaking process. In particular, as the photoresist forming process, it is desirable to perform heat treatment after exposure and heat treatment after development (post-baking treatment).

  The photoresist layer is, for example, a positive-type radiation-sensitive composition sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including excimer laser, electron rays, ion beams, X-rays and the like. Is preferably used. Among the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable. Specifically, a 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 characterized in that the quinonediazide group is decomposed to form a carboxyl group by irradiation with light having a wavelength of 500 nm or less, and as a result, the alkali-insoluble state becomes alkali-soluble. To use. Since this positive type photoresist has remarkably excellent resolution, it is used for manufacturing integrated circuits such as ICs (Integrated Circuits) and LSIs (Large Scale Integrations). Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products include “FHi622BC” (manufactured by FUJIFILM Electronic Materials Co., Ltd.).

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.3 to 2 μm. The positive radiation-sensitive composition may be applied by the above-mentioned curable composition application method.

  Then, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a group of resist through holes. The formation of the resist pattern is not particularly limited and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a group of resist through holes in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the cured product layer.

  The exposure of the photoresist layer is carried out by exposing the positive or negative radiation-sensitive composition via a predetermined mask pattern with g-line, h-line, i-line, etc., preferably i-line. You can After the exposure, the photoresist is removed in accordance with the area where the colored pattern is to be formed by developing the film with a developing solution.

  Any developer can be used as long as it does not affect the cured product layer and dissolves the exposed part of the positive resist and the uncured part of the negative resist. For example, a combination of various solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound in a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. The alkaline compound is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be mentioned. When an alkaline aqueous solution is used, it is generally washed with water after development.

  Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that a through hole group is formed in the cured product layer.

The dry etching is preferably performed by the following method from the viewpoint of forming a pattern cross section closer to a rectangle and further reducing damage to the support.
Using a mixed gas of a fluorine-based gas and an oxygen gas (O ₂ ), a first-stage etching in which etching is performed up to a region (depth) where the support is not exposed, and a nitrogen gas ( Second stage etching using a mixed gas of N ₂ ) and oxygen gas (O ₂ ) preferably to near the region (depth) where the support is exposed, and over-etching performed after the support is exposed. A method including and is preferred. Hereinafter, a specific method of dry etching, first-stage etching, second-stage etching, and overetching will be described.

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

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

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

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

  Then, the resist pattern (that is, the etching mask) remaining after the etching is removed. It is preferable that the removal of the resist pattern includes a step of applying a stripping solution or a solvent to the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern with cleaning water.

  Examples of the step of applying a stripping solution or solvent onto the resist pattern to make the resist pattern removable include, for example, a step of depositing the stripping solution or solvent on at least the resist pattern, and stagnating for a predetermined time to perform paddle development. Can be mentioned. The time for which the stripping solution or solvent is stagnant is not particularly limited, but is preferably several tens of seconds to several minutes.

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

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

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

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

  When removing with a stripper, it is sufficient that the resist pattern formed on the pattern is removed, and even if the deposition product that is an etching product adheres to the sidewall of the pattern, the deposition product is completely removed. You don't have to. The deposit is a product in which an etching product is attached and deposited on the side wall of the cured product layer.

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

<Solid-state image sensor>
The solid-state image sensor of the present invention has the optical filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the optical filter of the present invention and is not particularly limited as long as it functions as a solid-state imaging device. For example, the following configurations may be mentioned. .

A plurality of photodiodes forming a light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like are provided on a support, and the photodiode and the transfer electrode are provided on the transfer electrode. A light-shielding film made of tungsten or the like opened only in the light-receiving portion of the photodiode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, This is a configuration having the optical filter (color filter) of the present invention on the device protective film.
Further, a structure having a light collecting means (for example, a microlens, etc .; the same applies hereinafter) below the color filter (on the side close to the support) on the device protective film, or a structure having a light collecting means on the color filter. And so on.

<Image display device>
The optical filter and the color filter of the present invention can be used for an image display device such as a liquid crystal display device and an organic electroluminescence display device. The image display device provided with the color filter of the present invention can display a high-quality image in which the hue of the display image is good and the display characteristics are excellent. For definitions of display devices and details of each display device, see, for example, “Electronic display device (Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)”, “Display device (Junsho Ibuki, Sangyo Tosho Co., Ltd.) First year issued) "etc. The liquid crystal display device is described, for example, in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industrial Research Institute Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, liquid crystal display devices of various systems described in the above-mentioned “next-generation liquid crystal display technology”.

  The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd., 1996)". Further, the present invention is a lateral electric field driving method such as IPS (In Plane Switching), a liquid crystal display device with a wide viewing angle such as a pixel division method such as MVA (Multi-domain Vertical Alignment), and STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optical Compensated). The color filter of the present invention can also be applied to a COA (Color-filter On Array) system. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trend of market- (published by Toray Research Center, Research Division 2001)".

The liquid crystal display device provided with the color filter of the present invention is composed of 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 these known members. For these materials, see, for example, “The Market for Liquid Crystal Display Peripheral Materials / Chemicals (1994 Kentaro Shima Shima Co., Ltd., 1994)”, “Current status and future outlook for the 2003 liquid crystal related market (second volume)” Fuji Chimera Research Institute, Inc., 2003). "
Regarding the backlight, see SID meeting Digest 1380 (2005) (A. Konno et al.), Monthly display December 2005 issue, pages 18 to 24 (Yasuhiro Shima), pages 25 to 30 (Takaaki Yagi), etc. Have been described.

  Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "part" and "%" are based on mass unless otherwise specified. In the structural formulas below, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Pr represents a propyl group, and Ph represents a phenyl group.

<Measurement of weight average molecular weight>
The weight average molecular weight was measured in terms of polystyrene by GPC (Gel Permeation Chromatography) measurement.
Column type: TSKgel Super AWM-H (Tosoh product, 6.0 mm ID (inner diameter) x 15.0 cm)
Developing solvent: 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution column temperature: 50 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh HLC-8220GPC
Detector: RI (refractive index) detector calibration curve Base resin: polystyrene

<Synthesis of Compound Having Two or More Dye Structures and One or More Mercapto Group>
(Synthesis Example 1) Synthesis of dye B-1

<< Synthesis of Xanthene Compound (A-xt-1) >>
The following synthesis was carried out using a glass flask. Further, as the DCSF, one having a purity of 95% or more as measured by HPLC (liquid chromatography), which was crystallized by filtering through Celite after dissolving NMP, was used. In addition, 2,6-diisopropylaniline was used as a hydrochloride, which was purified by treatment with sodium hydroxide and had a purity of 95% or more as measured by HPLC.
DCSF (Spiro [3H-2,1-benzoxathiole-3,9 '-[9H] xanthene], 3', 6'-dichloro-, 1,1-dioxide, Chugai Kasei) 31 parts, 2,6-diisopropyl 67 parts of aniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask and stirred at an external temperature of 200 ° C. for 8 hours. Then, the mixture was allowed to cool to room temperature, the reaction solution was dropped into 600 parts of 2 mol / L hydrochloric acid water, and the precipitated crystals were separated by filtration. The crystals separated by filtration were dispersed and washed with 600 parts of acetonitrile at 40 ° C., and the crystals were collected by filtration and dried by blowing air for 10 hours to obtain 42.5 parts of Intermediate 1 (yield: 82%). .

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

<< Synthesis of Intermediate 3 >>
15 parts of pentafluorobenzenesulfonyl chloride and 300 parts of tetrahydrofuran (THF) were placed in the flask, and the internal temperature was cooled to -10 ° C. 6.8 parts of 28% ammonia water was added dropwise thereto so that the reaction liquid maintained at 0 ° C or lower. After dropping, the mixture was stirred for 1 hour at 0 ° C., and then the reaction solution was filtered. The obtained filtrate was concentrated under reduced pressure to remove THF, 100 parts of water was added, and the mixture was stirred. The obtained solid was filtered, washed with water, and then air-dried for 10 hours to obtain 11.7 parts (yield: 84%) of Intermediate 3.
5 parts of Intermediate 3, 18.0 parts of Intermediate 2, and 50 parts of methylene chloride were added to the flask and stirred at room temperature. 6.1 parts of triethylamine (TEA) was added to the flask and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was purified by column chromatography using a solvent of chloroform / ethyl acetate to obtain 11.1 parts (yield: 60%) of A-xt-1.

<Synthesis Example of Intermediate (S-3)>
22 parts of dipentaerythritol, 80.1 parts of sodium bromide, and 297 parts of dimethylacetamide were added to a three-necked flask, and the mixture was stirred in a nitrogen atmosphere at 0 ° C. in an ice bath. 122 parts of 6-bromohexanoyl chloride were washed with 16.5 parts of dimethylacetamide while being added dropwise to the reaction solution so that the temperature did not exceed 8 ° C, and then stirred at 15 ° C for 2 hours. The reaction solution was brought to 5 ° C., 55.4 parts of ethyl acetate was added, and then 110 parts of distilled water and 589 parts of 8% by mass sodium hydrogen carbonate solution were added little by little so as not to exceed 10 ° C. to stop the reaction. After the reaction liquid was returned to 20 ° C., liquid separation operation was performed. Subsequently, the organic layer was washed twice with 589 parts of 8 mass% sodium bicarbonate water and twice with 550 parts of 10 mass% sodium sulfate water. After adding sodium sulfate to the obtained organic layer, it was separated by filtration and the filtrate was concentrated under reduced pressure to obtain 107 parts (94%) of Intermediate S-1.
10.7 parts of Intermediate S-1, 31.4 parts of dimethylacetamide, and 1.09 parts of tetraethylammonium bromide were added to a three-necked flask and stirred under air at 10 ° C. To this, 6.5 parts of potassium thioacetate was added in 10 batches at 10 to 15 ° C., and the mixture was reacted at 50 ° C. for 3 hours. To this reaction solution, 47.9 parts of ethyl acetate, 54.4 parts of 4% by mass sodium hydrogen carbonate solution, and 26.7 parts of distilled water were added, and a liquid separation operation was performed. Subsequently, the organic layer was washed with 54.4 parts of 1 mol / L hydrochloric acid, 50.8 parts of 10 mass% saline and 50.8 parts of 25 mass% saline. After adding sodium sulfate to this organic layer, it was separated by filtration and the filtrate was concentrated under reduced pressure to obtain 9.9 parts of Intermediate S-2 (yield 95%).
8.9 parts of Intermediate S-2 and 23.5 parts of dimethylacetamide were added to a three-necked flask, and the mixture was stirred at 15 ° C under a nitrogen atmosphere. To this, 4.02 parts of hydrazine hydrochloride and 9.63 parts of sodium acetate were added while washing with 0.9 part of dimethylacetamide, and the mixture was reacted at 15 ° C. for 5 hours. Next, 67.3 parts of ethyl acetate and 38.2 parts of 2 mol / L hydrochloric acid water were added at 15 ° C. or lower, the temperature was raised to 20 ° C., and liquid separation operation was performed. The organic layer was washed twice with 38.2 parts of 1 mol / L hydrochloric acid water and then 39.3 parts of 9.1% by mass saline, and magnesium sulfate was added to the organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure. By doing so, 6.6 parts of Intermediate S-3 was obtained (yield 92%).

<Synthesis Example of Dye B-1>
31.0 parts of Intermediate S-3 was dissolved in 445 parts of 1,3-dimethyl-2-imidazolidinone (DMI), and 93.34 parts of A-xt-1 was added to 49. It was added at 20 ° C. while washing with 7 parts of DMI. To this reaction solution, 15.5 parts of diazabicycloundecene (DBU) was added at 20 to 30 ° C. while washing with 1.55 parts of DMI. This reaction solution was stirred at 25 ° C for 1 hour, and then 18.3 parts of acetic acid was added at 20 to 30 ° C while washing with 1.83 parts of DMI. This reaction liquid was added dropwise to a mixed liquid of 1014 parts of methanol and 427 parts of distilled water for reprecipitation, and the obtained crystals were filtered to obtain 120 parts of dye B.
It was confirmed that the ratio n of the dye site to the R site in NMR (nuclear magnetic resonance) measurement was 3.5. Moreover, the weight average molecular weight of the dye B-1 was 7,600.

(Synthesis Example 2) Synthesis of Dye B-2 Intermediate S-3 of Synthesis Example 1 was changed to the following Intermediate S-5 so that the ratio of dye moieties (values of m and n) was as described. Synthesis was performed in the same manner as in Synthesis Example 1 except that the mass of each raw material was changed. It was confirmed that the ratio n of the dye site to the R site in the NMR measurement was 3.5. The weight average molecular weight of the dye B-2 was 7,400.

<< Synthesis of (Intermediate S-5) >>
15 parts of dipentaerythritol, 270 parts of dehydrated DMF (N, N-dimethylformamide) and 86 parts of allyl bromide were added to a three-necked flask, and the mixture was stirred in a water bath at 20 ° C. under a nitrogen atmosphere. After adding 35 parts of sodium hydride (60% oil dispersion) so that the temperature did not exceed 35 ° C, the mixture was stirred at room temperature for 2 hours. After the reaction solution was gradually added to 200 parts of 1 mol / L hydrochloric acid water to stop the reaction, 200 parts of ethyl acetate was added to carry out a liquid separation operation. Subsequently, the organic layer was washed with 200 parts of 1 mol / L hydrochloric acid water, 200 parts of water, and 200 parts of saturated saline solution. After adding sodium sulfate to the obtained organic layer, it was filtered off and the filtrate was concentrated under reduced pressure to obtain 28 parts of Intermediate S-4.
Subsequently, 25 parts of Intermediate S-4 and 58 parts of thioacetic acid were dissolved in 125 parts of dehydrated THF (tetrahydrofuran), stirred for 30 minutes at 70 ° C. under a nitrogen atmosphere, and then 2 parts of azobisisobutyronitrile was added, The mixture was stirred at 70 ° C for 4 hours. The obtained reaction solution was concentrated under reduced pressure, dehydrated methanol was added, and 19 parts of sodium methoxide (28% methanol solution) was added. After 1 hour, the reaction solution was added dropwise to 120 parts of 1 mol / L hydrochloric acid water while cooling in an ice bath, 200 parts of ethyl acetate was added, and a liquid separation operation was performed. Subsequently, the organic layer was washed with 200 parts of 1 mol / L hydrochloric acid water, 200 parts of water, and 200 parts of saturated saline solution. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure to obtain 13 parts of Intermediate S-5.

(Synthesis Example 3) Synthesis of dye B-3

(A-xt-1) of Synthesis Example 1 was changed to a mixture of (A-xt-1) and (A-tp-1), and the ratio of dye moieties (values of m, n, and k) was described. Synthesis was performed in the same manner as in Synthesis Example 1 except that the mass of each raw material was changed so as to be as described above. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.0 and k was 0.5. The weight average molecular weight of the dye B-3 was 7,500.

(Synthesis Example 4) Synthesis of dye B-4

(A-xt-1) in Synthesis Example 1 was changed to (A-xt-3), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 4. The weight average molecular weight of Dye B-4 was 8000.

(Synthesis example 5) Synthesis of dye B-5

6.6 parts of Intermediate S-6, 32.5 parts of (A-xt-5), and 50 g of N-ethylpyrrolidone were heated at 80 ° C. under a nitrogen atmosphere. Next, 2,2′-azobis (isobutyric acid) dimethyl) [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] (0.6 g) was added, and the mixture was heated and stirred for 5 hours. The reaction solution was allowed to cool to 20 ° C., dropped into a mixed solution of 202 parts of methanol and 86 parts of distilled water and reprecipitated, and the obtained crystals were filtered to obtain 38.0 parts of Dye B-5. Got It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.0. The weight average molecular weight of Dye B-5 was 5,500.

(Synthesis example 6) Synthesis of dye B-6

  (A-xt-1) in Synthesis Example 1 was changed to (A-tp-1), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.75. The weight average molecular weight of Dye B-6 was 7,700.

(Synthesis Example 7) Synthesis of dye B-7

(A-xt-1) in Synthesis Example 1 was changed to (A-tp-2), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed that the ratio n of the dye moiety to the R moiety in the NMR measurement was 3.65. The weight average molecular weight of Dye B-7 was 7,700.

(Synthesis Example 8) Synthesis of dye B-8

(A-xt-1) in Synthesis Example 1 was changed to (A-aq-1), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.65. The weight average molecular weight of Dye B-8 was 4000.

(Synthesis example 9) Synthesis of dye B-9

(A-xt-1) in Synthesis Example 1 was changed to (A-az-1), Intermediate S-3 was changed to the following Intermediate S-7, and the ratio of dye moieties (values of m and n). Was synthesized in the same manner as in Synthesis Example 1 except that the mass of each raw material was changed so that It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 2.5. The weight average molecular weight of Dye B-9 was 4000.

(Synthesis example 10) Synthesis of dye B-10

(A-xt-1) in Synthesis Example 1 was changed to (A-sq-1), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.75. The weight average molecular weight of Dye B-10 was 5,500.

(Synthesis example 11) Synthesis of dye B-11

(A-xt-5) in Synthesis Example 5 was changed to (A-Pc-1), Intermediate S-6 was changed to the following Intermediate S-8, and the ratio of dye moieties (values of m and n). Was synthesized in the same manner as in Synthesis Example 1 except that the mass of each raw material was changed so that It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.50. The weight average molecular weight of Dye B-11 was 8,200.

(Synthesis Example 12) Synthesis of dye B-12

(A-xt-1) in Synthesis Example 1 was changed to (A-am-1), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.60. The weight average molecular weight of dye B-12 was 7,200.

(Synthesis Example 13) Synthesis of dye B-13

(A-xt-1) in Synthesis Example 1 was changed to a mixture of (A-am-1) and (A-Pc-2), and the ratio of dye moieties (values of m, n, and k) was as described. Synthesis was performed in the same manner as in Synthesis Example 1 except that the mass of each raw material was changed so that It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 2.0 and k was 2.0. The weight average molecular weight of Dye B-13 was 8,100.

(Synthesis Example 14) Synthesis of dye B-14

(A-xt-1) in Synthesis Example 1 was changed to (A-subPc-1), Intermediate S-3 was changed to Intermediate S-9, and the ratio of dye moieties (values of m and n) was described. Synthesis was performed in the same manner as in Synthesis Example 1 except that the mass of each raw material was changed so as to be as described above. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 2.00. The weight average molecular weight of Dye B-14 was 3,300.

(Synthesis example 15) Synthesis of dye B-15

(A-xt-1) in Synthesis Example 1 was changed to (A-Qu-1), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.40. The weight average molecular weight of Dye B-14 was 6,500.

(Synthesis example 16) Synthesis of dye B-16

(A-xt-1) of Synthesis Example 1 was changed to (A-pm-1), and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Was synthesized in the same manner as in Synthesis Example 1. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.80. The weight average molecular weight of Dye B-14 was 7,400.

(Synthesis Example 17) Synthesis of dye B-17
Cyclohexanone (15.6 parts) was added to the three-necked flask, and the mixture was heated to 90 ° C. under a nitrogen atmosphere. 17.5 parts of (A-xt-5), 2.41 parts of methacrylic acid (MAA), 1.38 parts of 28 mmol dodecyl mercaptan, 5.52 parts of Monomer 1 and 2,2'- were added to this solution. A mixed solution of azobis (isobutyric acid) dimethyl) [trade name: V601, manufactured by Wako Pure Chemical Industries, Ltd.] 6.25 parts and cyclohexanone 40.6 parts was added dropwise over 1 hour. Thereafter, the mixture was stirred at 90 ° C. for 3 hours, cooled to room temperature, dropped into a mixed solvent of ethyl acetate / acetonitrile = 750 mL / 85 mL, and reprecipitated. The obtained crystals were separated by filtration and blow-dried at 40 ° C. for 1 day to obtain 15.2 parts of B-17-1.
To 15.2 parts of B-17-1 obtained above, 125 parts of dimethylacetamide (DMAc) was added, and 1.38 parts of hydrazine hydrochloride and 3.29 parts of sodium acetate were added at 15 ° C under a nitrogen atmosphere. Was added, and the mixture was stirred at 15 ° C. for 5 hours. To this reaction solution, 250 parts of 2 mol / L hydrochloric acid was added at 15 ° C or lower, and the obtained crystals were separated by filtration and blow-dried at 40 ° C for 1 day to obtain 12 parts of B-17. B-17 had an acid value of 1.02 mmol / g, and when the composition ratio (molar ratio) was confirmed by ¹ H-NMR, it was found that the dye part: methacrylic acid part: thiol part = 26: 45: 29. The weight average molecular weight of B-17 was 12,000.

(Synthesis Example 18) Synthesis of dye B-18

Polymerization of (A-xt-5), methacrylic acid, and monomer 1 of Synthesis Example 17 was changed to polymerization of monomer 2 and monomer 1, and the charged amount was changed so that the composition ratio (molar ratio) was as described. Except for the above, it was synthesized in the same manner as in Synthesis Example 17. The weight average molecular weight of the dye B-18 was 11,000.

(Synthesis example 19) Synthesis of dye B-19

Polymerization of (A-xt-5), methacrylic acid, and monomer 1 of Synthesis Example 17 was changed to polymerization of monomer 3 and monomer 4, and the charging amount was changed so that the composition ratio (molar ratio) was as described. Synthesis was performed in the same manner as in Synthesis Example 17 except that the above was performed. The weight average molecular weight of the dye B-19 was 9,000.

(Synthesis example 20) Synthesis of dye B-20
Synthesis except that (A-xt-5) in Synthesis Example 5 was changed to (X-1) and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Synthesized as in Example 5. It was confirmed that the ratio n of the dye moiety to the R moiety in the NMR measurement was 3.85. The weight average molecular weight of Dye B-20 was 7,100.

(Synthesis example 21) Synthesis of dye B-21
Synthesis except that (A-xt-5) in Synthesis Example 5 was changed to (X-2) and the mass of each raw material was changed so that the ratio of dye moieties (values of m and n) was as described. Synthesized as in Example 5. It was confirmed by NMR measurement that the ratio n of the dye site to the R site was 3.65. The weight average molecular weight of Dye B-21 was 6,400.

(Synthesis example 22) Synthesis of dye B-22
Polymerization of (A-xt-5), methacrylic acid, and monomer 1 of Synthesis Example 17 was changed to polymerization of monomer 3 and monomer 5, and the charging amount was changed so that the composition ratio (molar ratio) was as described. Synthesis was performed in the same manner as in Synthesis Example 17 except that the above was performed. The weight average molecular weight of the dye B-22 was 11,000.

(Synthesis Example 23) Synthesis of dye B-23
8.72 parts of (A-xt-6) and 2.50 parts of isocyanate compound 1 (methylenediphenyl 4,4'-diisocyanate) were dissolved in propylene glycol monomethyl ether acetate (PGMEA) (46.7 g). And heated to 80 ° C. under a nitrogen atmosphere. Next, 0.002 part of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was added, and the mixture was heated for 10 hours and then cooled to room temperature. This reaction solution was reprecipitated with 100 parts of hexane, the obtained crystals were filtered off, and dried by blowing with air at 40 ° C. to obtain 10.3 parts of (B-23-1).
Dye B-23 was synthesized in the same manner as (B-17-1) of Synthesis Example 17 from (B-23-1) in the same manner as in the synthesis of dye B-17.

<Preparation of resist solution for undercoat layer>
The components having the following composition were mixed and dissolved, and then filtered through a 0.45 μm nylon filter to prepare a resist solution for undercoat layer.
-Composition of resist liquid for undercoat layer-
-Solvent (propylene glycol monomethyl ether acetate (PGMEA)): 19.20 parts-Solvent (ethyl lactate): 36.67 parts-Alkali-soluble resin (benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer) (Molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) 40% PGMEA solution: 30.51 parts Curable compound (dipentaerythritol hexaacrylate (KAYARAD DPHA, sartomer) Company): 12.20 parts-Polymerization inhibitor (p-methoxyphenol): 0.0061 parts-Fluorosurfactant (Megafuck F475, manufactured by DIC Corporation): 0.83 parts-Photopolymerization initiator (Trihalomethyltriazine-based photopolymerization initiator, TAZ-107, manufactured by Midori Kagaku Co., Ltd. ): 0.586 copies

<Production of silicon wafer substrate with undercoat layer>
A silicon wafer having a diameter of 6 inches (1 inch = 25.4 mm) was heat-treated in an oven at 200 ° C. for 30 minutes. Then, the above-mentioned undercoating resist solution was applied onto this silicon wafer so that the dry film thickness was 1.5 μm, and further dried by heating in an oven at 220 ° C. for 1 hour to form an undercoating layer. A silicon wafer substrate was obtained.

<Preparation of curable composition>
The following components were mixed, dispersed, dissolved, and filtered with a 0.45 μm nylon filter to obtain a curable composition.

(Composition 1)
-Organic solvent (cyclohexanone): 17.12 parts-Curable compound (epoxy compound) described in the following table: 4.395 parts-Cyclohexanone solution of the dye described in the following table (solid content concentration 12.3%): 39 0.000 part-Pigment dispersion described in the table below (solid content concentration 12.8%): 36.97 part-Polymerization inhibitor (p-methoxyphenol): 0.0007 part-Fluorine-based surfactant (Megafuck) F475, manufactured by DIC Corporation, 1% PGMEA solution): 2.50 parts

(Composition 2)
-Organic solvent (cyclohexanone): 17.12 parts-Curable compound (epoxy compound): 4.395 parts-Cyclohexanone solution of dye 1 described in the following table (solid content concentration 12.3%): 24.57 parts- Cyclohexanone solution of Dye 2 shown in the table below (solid content concentration 12.3%): 51.40 parts-Polymerization inhibitor (p-methoxyphenol): 0.0007 parts-Fluorine-based surfactant (Megafuck F475, DIC Corporation, 1% PGMEA solution): 2.50 parts

(Composition 3)
-Organic solvent (cyclohexanone): 25.22 parts-Alkali-soluble resin 1 (solid content concentration 30.6%) shown in the table below: 0.62 parts (solid 0.19 parts)
Alkali-soluble resin 2 (Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd., solid concentration 41.7%): 0.12 parts (solid 0.05 parts)
-Photopolymerization initiator described in the following table: 0.59 part-Cyclohexanone solution of the dye described in the following table (solid content concentration 12.3%): 35.5 parts-Pigment dispersion liquid (solid Minute concentration 12.8%): 33.2 parts-Curable compound (polymerizable compound) shown in the following table: 1.90 parts-Curable compound (epoxy compound) shown in the following table: 0.35 parts- Polymerization inhibitor (p-methoxyphenol): 0.0009 parts-Fluorine-based surfactant (1% PGMEA solution of the following mixture (Mw = 14000)): 2.50 parts

(Composition 4)
-Organic solvent (cyclohexanone): 14.69 parts-Alkali-soluble resin 1 (solid content concentration 30.6%) described in the table below: 0.29 part (solid 0.09 part)
-Alkali-soluble resin 2 (Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd., solid content concentration 41.7%): 0.05 part-Photopolymerization initiator described in the following table: 0.78 part- Cyclohexanone solution of dye 1 described (solid content concentration 12.3%): 28.45 parts. Cyclohexanone solution of dye 2 described in the following table (solid content concentration 12.3%): 51.23 parts. Curable compound (polymerizable compound) described: 1.61 part Curable compound (epoxy compound) described in the following table: 0.39 part Polymerization inhibitor (p-methoxyphenol): 0.0007 part Fluorine -Based surfactant (Megafuck F475, 1% PGMEA solution manufactured by DIC Corporation): 2.50 parts

<Production of color filter>
(Production Example 1) Pattern formation by dry etching method The curable composition obtained above was applied onto a 7.5 cm x 7.5 cm glass substrate using a spin coater to a film thickness of 0.5 µm. Then, using a hot plate, heating was performed at 200 ° C. for 5 minutes to cure the coating film to form a cured film layer. The film thickness of this cured film layer was 0.5 μm.
Then, a positive photoresist "FHi622BC" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied and prebaked at 90 ° C. for 1 minute to form a photoresist layer having a film thickness of 0.8 μm.
Subsequently, the photoresist layer was pattern-exposed using an i-line stepper (manufactured by Canon Inc.) with an exposure dose of 350 mJ / cm ² , and the temperature of the photoresist layer or the ambient temperature was 90 ° C. for 1 minute. , Heat treatment was performed. Thereafter, a developing solution "FHD-5" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was developed for 1 minute, and a post-baking treatment was further carried out at 110 ° C for 1 minute to form a resist pattern. The size of this resist pattern was set to 1.0 μm on each side in consideration of etching conversion difference (reduction of pattern width due to etching).
Next, the obtained glass substrate was attached to a silicon wafer having a diameter of 8 inches (1 inch = 25.4 mm), and RF (high frequency) power was applied by a dry etching device (U-621, manufactured by Hitachi High-Technologies Corporation). : 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C., gas type and flow rate of mixed gas CF ₄ : 80 mL / min, O ₂ : 40 mL / min, Ar: 800 mL / min. As a result, the 80-second first stage etching process was performed.
Next, in the same etching chamber, RF (high frequency) power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas type and flow rate of mixed gas were set. N ₂ : 500 mL / min, O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10), 28 second second-stage etching treatment, over-etching treatment did.
After performing dry etching under the above conditions, a photoresist stripping solution "MS230C" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform stripping treatment at 50 ° C. for 120 seconds to remove the resist, thereby forming a colored pattern. Was formed. Further, cleaning with pure water and spin drying were carried out, and then dehydration baking treatment was carried out at 100 ° C. for 2 minutes. As described above, a color filter was obtained.

(Production Example 2) Pattern formation by photolithography method The curable composition obtained above was applied onto the undercoat layer of the silicon wafer substrate with the undercoat layer prepared above to form a coating film. Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of this coating film was 1 μm.
Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at a wavelength of 365 nm through an Island pattern mask having a 1.0 μm square pattern at an exposure amount of 50 to 1200 mJ / cm ² .
After that, the substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film Electronics Material). Paddle development was performed for 60 seconds at 23 ° C. to form a colored pattern on the substrate.
The substrate on which the colored pattern is formed is fixed on a horizontal rotary table by a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is supplied from above the center of rotation in the form of a shower from a jet nozzle. Then, the substrate was rinsed, spin-dried, and post-baked on a hot plate at 200 ° C. for 300 seconds to obtain a colored pattern (color filter) having a film thickness of 1 μm.
As described above, a silicon wafer with a colored pattern having a configuration in which the colored pattern (color filter) was provided on the undercoat layer of the silicon wafer substrate with the undercoat layer was obtained.

<Evaluation method>
(Color transfer evaluation)
The absorbance of the colored pattern in each color filter was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance A).
Next, a CT-2000L solution (a transparent base material manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to the colored pattern forming surface of the color filter whose absorbance A was measured so that the dry film thickness was 1 μm, and dried. After forming a transparent film, heat treatment was performed at 280 ° C. for 5 minutes. After completion of heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance B).
Regarding the value of the absorbance B of the obtained transparent film, the ratio [%] to the value of the absorbance A of the colored pattern measured before heating was calculated [the following (formula A)]. This was used as an index for evaluating color transfer to adjacent pixels.
(Formula A) Color transfer (%) = (Absorbance B / Absorbance A) × 100
A: less than 1% B: 1% or more and less than 3% C: 3% or more and less than 5% D: 5% or more

(chemical resistance)
Each curable composition was applied onto a 7.5 cm × 7.5 cm glass substrate using a spin coater so as to form a coating film having a film thickness of 0.6 μm, and using a hot plate at 100 ° C. The coating film was heated and dried for 2 minutes, and the coating film was cured at 200 ° C. for 8 minutes to form a cured film. The spectroscopic spectrum of the obtained cured film was measured.
Next, the obtained cured film was immersed in cyclohexanone at 25 ° C. for 10 minutes, rinsed with running water, and then the spectrum of the cured film was measured.
The absorbance before and after immersion in cyclohexanone was compared, the dye residual ratio after immersion was calculated from the following formula, and evaluated according to the following categories. It should be noted that the higher the numerical value of the residual dye rate, the better the chemical resistance.
Dye residual rate (%) = (maximum absorbance of cured film after immersion in cyclohexanone / maximum absorbance before immersion in cyclohexanone) × 100
A: Dye residual rate = 95% or more and 100% or less B: Dye residual rate = 90% or more and less than 95% C: Dye residual rate = 85% or more and less than 90% D: Dye residual rate = 50% or more and less than 85% E: Dye residual rate = 0% or more and less than 50%

  As shown in the above table, in the examples, color transfer was difficult and the chemical resistance was excellent. On the other hand, in the comparative example, color transfer was likely to occur, and further, the chemical resistance was poor.

The materials listed in the above table are as follows.
Dyes B-1 to B-23: Dyes B-1 to B-23 described above.
Comparative dyes 1-4: the following structures.

(Pigment dispersion P1)
The pigment dispersion liquid P1 was prepared as follows.
C. I. Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as "PB15: 6") 19.4 parts by mass (average primary particle diameter 55 nm), and a dispersant (Disperbyk-161, manufactured by BYK Chemie) 2.95 parts by mass. Parts, alkali-soluble resin J1 (benzyl methacrylate / methacrylic acid copolymer, 30% PGMEA solution) in terms of solid content of 2.95 parts by mass (solution 9.93 parts by mass), PGMEA from 165.3 parts by mass. The mixed solution was mixed and dispersed by a bead mill (zirconia beads 0.3 mm diameter) for 3 hours. Thereafter, a dispersion treatment was further performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism 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 P1. With respect to the obtained pigment dispersion P1, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm. It was

(Pigment dispersion P2)
In the preparation of the pigment dispersion P1, a pigment dispersion P2 was prepared by the same operation except that the following dispersant D1 was used as the pigment dispersant.
Mw = 20000, x / y = 50/50 (mass ratio), n = 20, acid value = 100 mgKOH / g

(Pigment dispersion P3)
Pigment Dispersion Liquid P3 was prepared in the same manner as in Pigment Dispersion Liquid P1 except that the following Dispersant D2 was used as the pigment dispersant.
Mw = 20000, x / y = 15/85 (mass ratio), n = 20, acid value = 100 mgKOH / g

(Pigment dispersion P4)
In the preparation of the pigment dispersion P1, C.I. I. Pigment Dispersion Liquid P4 was prepared in the same manner as Pigment Dispersion Liquid P1 except that Pigment Red 254 was used. The average primary particle diameter of the pigment was 26 nm when measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)).

(Pigment dispersion P5)
In the preparation of the pigment dispersion P1, C.I. I. Pigment Dispersion Liquid P5 was prepared in the same manner as Pigment Dispersion Liquid P1 except that Pigment Green 58 was used. The average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 30 nm.

(Pigment dispersion P6)
In the preparation of the pigment dispersion P1, C.I. I. Pigment Dispersion Liquid P6 was prepared in the same manner as Pigment Dispersion Liquid P1 except that Pigment Yellow 139 was used. The average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and it was 27 nm.

(Photopolymerization initiator)
(I1) to (I7), (I9): the following structures. The following (I1) is IRGACURE (registered trademark) -OXE01, (I2) is IRGACURE (registered trademark) -OXE02 (manufactured by BASF), (I3) is IRGACURE (registered trademark) -379, (I4) is DAROCUR (registered trademark). -TPO (all of which are manufactured by BASF).
(I8): ADEKA ARKUL'S NCI-831 (made by ADEKA)

Alkali-soluble resin: Structure below

Curable compound (polymerizable compound)
Z1: ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Z2: dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Z3: Ethoxylated (4) pentaerythritol tetraacrylate, SR494 (manufactured by Sartomer)
Z4: ethoxylated (3) trimethylolpropane triacrylate, SR454 (manufactured by Sartomer)
Z5: ethoxylated (6) trimethylolpropane triacrylate, SR499 (manufactured by Sartomer)

Curable compound (epoxy compound)
E1: EHPE3150 (manufactured by Daicel Corporation)
E2: EPICLON HP-4700 (manufactured by DIC Corporation)
E3: EPICLON HP-4032D (manufactured by DIC Corporation)
E4: Structure below

Claims (13)

A compound A having two or more dye structures and one or more mercapto groups,
And a curable compound having two or more curable groups,
The dye structure, triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, thiazole dye structure, pyrazolo At least one dye structure selected from a triazole dye structure and a dipyrromethene dye structure,
The compound A contains at least one of a repeating unit represented by the following formula (A), a repeating unit represented by the formula (B) and a repeating unit represented by the formula (C), and has a mercapto group. Or a compound having
Or a compound represented by formula (D):
The curable compound includes a curable compound having two or more epoxy groups,
20 to 95% by mass of the compound A in the total solid content of the curable composition,
The content of the curable compound having two or more epoxy groups is 0.1 to 50 mass% with respect to the total solid content of the curable composition,
A curable composition in which the weight average molecular weight of the compound A is 2,000 or more.
In formula (A), X ¹ represents a main chain of a repeating unit, L ¹ represents a single bond or a divalent linking group, and D ¹ represents the dye structure;
In formula (B), X ² represents a main chain of a repeating unit, L ² represents a single bond or a divalent linking group, D ² represents the dye structure, and Y ² and an ionic bond or a coordinate bond. Represents a dye structure having a possible group, Y ² represents a group capable of forming an ionic bond or a coordinate bond with D ² .
In the formula (C), L ³ represents a single bond or a divalent linking group, D ³ is the dye structure, which is a triarylmethane dye structure, a xanthene dye structure represented by the following formula (J), and anthraquinone. Dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, thiazole dye structure, pyrazolotriazole dye structure, and dipyrromethene dye structure. Represents a structure, m represents 0 or 1;
In formula (D), L ⁴ represents a (n + k + q) -valent linking group, L ^{11 to} L ¹³ each independently represent a single bond or a divalent linking group, and D ⁴ represents the dye structure. , Triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure represented by any of the following formulas (AQ-1) to (AQ-3), cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure , A subphthalocyanine dye structure, an azo dye structure, a thiazole dye structure, a pyrazolotriazole dye structure and a dipyrromethene dye structure, and SH represents a mercapto group, and P ¹ represents a mercapto group other than Represents a substituent; n represents an integer of 2 to 15, k represents an integer of 0 to 13, and q represents an integer of 0 to 12; If ^{the 4} dye structure represented by the no mercapto group, n represents. 2 to 14, k represents 1 to 13, q represents an 0~12, n + k + q represents 3 to 15; ^{D 4} When the represented dye structure has a mercapto group, n represents 2 to 15, k represents 0 to 13, q represents 0 to 12, and n + k + q represents 2 to 15.
In formula (J), R ⁸² and R ⁸³ are a hydrogen atom or a substituted or unsubstituted alkyl group, R ⁸¹ and R ⁸⁴ are a substituted or unsubstituted alkyl group, and R ⁸⁵ is independently a monovalent group. Represents a substituent, and m represents an integer of 0 to 5. X represents a counter anion. When X is absent, at least one of R ^{81 to} R ⁸⁵ contains an anion.
In formula (AQ-1), A and B each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom. Xqa represents ORqa ¹ or NRqa ² Rqa ³ . Rqa ^{1 to} Rqa ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rq _{1 to} Rq ₄ represent a substituent. Ra and Rb each independently represent a hydrogen atom, an alkyl group or an aryl group.
In formula (AQ-2), C and D each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom. Xqb represents ORqb ¹ or NRqb ² Rqb ³ . Rqb ^{1 to} Rqb ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rq _{5 to} Rq ₈ represent a substituent. Rc represents a hydrogen atom, an alkyl group or an aryl group.
In formula (AQ-3), E and F each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom. Xqc represents ORqc ¹ or NRqc ² Rqc ³ . Rqc ^{1 to} Rqc ³ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rq _{9 to} Rq ₁₂ represent a substituent. Rd represents a hydrogen atom, an alkyl group or an aryl group. In the formula (D), when the dye structure represented by D ⁴ does not have a mercapto group, n represents 3 to 14, k represents 1 to 10, q represents 0 to 12, and n + k + q represents 4 to 4. represents 15, if the dye structure represented by ^{D 4} is a mercapto group, n represents 3 to 15, k represents 0, q represents 0~12, n + k + q represents 3-15, The curable composition according to claim 1. The curable composition according to claim 1, wherein n in the formula (D) represents 2 to 14 , k represents 1 to 13, q represents 0 to 12, and n + k + q represents 3 to 15. The curable composition according to claim 1, wherein the compound represented by the formula (D) is a compound represented by the following formula (D-1).
In formula (D-1), L ⁴ represents a (n + k + q) -valent linking group. n represents an integer of 2 to 15, k represents an integer of 0 to 13, and q represents an integer of 0 to 12. D ⁴ represents a dye structure similar to D ⁴ in the formula (D) , SH represents a mercapto group, P ¹ is a substituent other than a mercapto group, and is an acid group, a curable group, or , Represents a monovalent polymer chain having a repeating unit . B ^{1 to} B ³ are each independently a single bond, —O—, —S—, —CO—, —NR—, —O ₂ C—, —CO ₂ —, —NROC—, or —CONR—. Represents R represents a hydrogen atom, an alkyl group or an aryl group. C ^{1 to} C ³ each independently represent a single bond or a divalent linking group. S represents a sulfur atom. When n is 2 or more, the plurality of D ⁴ may be different from each other or may be the same. When q is 2 or more, the plurality of P ¹ may be different from each other or may be the same. When the dye structure represented by D ⁴ does not have a mercapto group, n represents 2 to 14 , k represents 1 to 13, q represents 0 to 12, and n + k + q represents 3 to 15. When the dye structure represented by D ⁴ has a mercapto group, n represents 2 to 15, k represents 0 to 13, q represents 0 to 12, and n + k + q represents 2 to 15.   The curable composition according to any one of claims 1 to 4, comprising a curable compound having an ethylenically unsaturated group as the curable compound, and further containing a photopolymerization initiator.   The compound A is a compound having at least one of the repeating unit represented by the formula (A) and the repeating unit represented by the formula (C) and having a mercapto group, or a compound represented by the formula (D ] The curable composition of any one of Claims 1-5 which is a compound represented by these. The curable composition according to any one of claims 1 to 6, wherein the compound A contains a repeating unit represented by the formula (E);
In formula (E), X ⁵ represents a main chain of a repeating unit, L ⁵ represents a single bond or a divalent linking group, and SH represents a mercapto group.   The curable composition according to claim 1, which is used for forming a colored layer of a color filter.   An optical filter using the curable composition according to claim 1.   A color filter using the curable composition according to claim 1.   A step of forming a curable composition layer on a support using the curable composition according to claim 1, and a curable composition layer formed by a photolithography method or a dry etching method. And a step of forming a pattern with respect to the pattern forming method.   A solid-state image sensor having the optical filter according to claim 9.   An image display device comprising the optical filter according to claim 9.