JP2013163753A - Color developer and color developing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color developer excellent in black color formation.SOLUTION: A color developer includes an azine-based compound represented by general formula (1) as a color component, wherein R-Rrepresent each independently a hydrogen atom, alkyl group, aralkyl group, heterocyclic group, or aryl group. Rand Rrepresent each independently a substituent group; X represents an oxygen atom, sulfur atom, or NR; Rrepresents a hydrogen atom, alkyl group, or aryl group; Rrepresents a group having a carbonyl group or sulfonyl group; and m and n represent each independently an integer of 0-3.

Description

  The present invention relates to a color former, a method for forming a color film or an image using the color former, and an azine color-forming compound used therefor.

  An azine compound is known as an oxidative coloring leuco dye. For example, Patent Document 1 discloses that an image is formed by electrochromism using a phenothiazine compound and a phenoxazine compound.

JP 61-44955 A

An object of the present invention is to provide a color former excellent in black color developability. Another object of the present invention is to provide a color former capable of forming a black color or forming an image stably on a curved surface by coating the color former and coloring it.
Another object of the present invention is to provide a method for forming a color developing film or an image using the color former.
Furthermore, an object of the present invention is to provide an azine compound suitable as a color forming component of the color former.

The above problems of the present invention have been achieved by the following means.
<1> A color former containing an azine compound represented by the following general formula (1) as a color former.

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, a heterocyclic group or an aryl group. R ⁵ and R ⁶ each independently represent a substituent. X represents an oxygen atom, Represents a sulfur atom or NR ⁸ , R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents a group having a carbonyl group or a sulfonyl group, and m and n each independently represents an integer of 0 to 3. .)
<2> The color former according to <1>, wherein the azine-based compound is represented by the following general formula (2a).

(In the formula, R ⁵ , R ⁶ , R ⁷ , m and n are as defined in the general formula (1). R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. Y represents Represents an oxygen atom or a sulfur atom.)
<3> The color former according to <1>, wherein the azine-based compound is represented by the following general formula (2b).

(In formula, R < ⁵ >, R < ⁶ >, R < ⁷ >, m, and n are synonymous with the said General formula (1). R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, or an aryl group each independently. R < ²⁸ >. Represents a hydrogen atom, an alkyl group or an aryl group.)
<4> The color former according to any one of <1> to <3>, which develops a black color.
<5> The color former according to any one of claims 1 to 4, which develops color when irradiated with light.
<6> The color former according to any one of <1> to <5>, which contains a color former.
<7> The color former according to any one of <1> to <6>, comprising a photopolymerizable monomer and a photopolymerization initiator.
<8> The color former according to any one of <1> to <7>, which is for image formation.
<9> Formation of a coloring film or an image including a step of forming a film using the color former according to any one of <1> to <8>, and a step of irradiating the film with all light to cause color development Method.
<10> An azine-based compound represented by the following general formula (1).

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, a heterocyclic group or an aryl group. R ⁵ and R ⁶ each independently represent a substituent. X represents an oxygen atom, Represents a sulfur atom or NR ⁸ , R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents a group having a carbonyl group or a sulfonyl group, and m and n each independently represents an integer of 0 to 3. .)
<11> The azine compound according to <10>, represented by the following general formula (2a).

(In the formula, R ⁵ , R ⁶ , R ⁷ , m and n are as defined in the general formula (1). R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. Y represents Represents an oxygen atom or a sulfur atom.)
<12> The azine compound according to <10>, represented by the following general formula (2b).

(In formula, R < ⁵ >, R < ⁶ >, R < ⁷ >, m, and n are synonymous with the said General formula (1). R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, or an aryl group each independently. R < ²⁸ >. Represents a hydrogen atom, an alkyl group or an aryl group.)

  In this specification, when there are a plurality of substituents, linking groups, ligands, etc. (hereinafter referred to as substituents) indicated by specific symbols, or a plurality of substituents etc. are specified simultaneously or alternatively. In some cases, each substituent group may be the same as or different from each other. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are close to each other, they may be connected to each other or condensed to form a ring.

  The color former of the present invention develops a black color when irradiated with light and has excellent colorability. Since the color former of the present invention can be coated to cause color development, it can be colored or imaged on a curved surface with good reproducibility. The azine compound of the present invention is suitable as a color forming component of the color former of the present invention.

[Coloring agent of the present invention]
The color former of the present invention contains a specific azine compound as a black color developing component.
(Azine compounds)
The azine compound contained in the color former of the present invention is represented by the following general formula (1).

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, an aralkyl group, a heterocyclic group, or an aryl group. R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a heterocyclic ring containing at least a nitrogen atom as a ring constituent atom. In addition, the heterocyclic ring may have an unsaturated bond.
In the general formula (1), R ⁵ and R ⁶ represent a substituent.
In the general formula (1), X represents an oxygen atom, a sulfur atom and NR ⁸ .
R ⁸ represents a hydrogen atom, an alkyl group or an aryl group.
In the general formula (1), R ⁷ represents a group having a carbonyl group or a sulfonyl group.
In said general formula (1), m and n represent the integer of 0-3, Preferably it is an integer of 0-2.
Hereinafter, the general formula (1) will be described more specifically.

-Substituents R ¹ , R ² , R ³ , and R ^4-
In the general formula (1), when one or more of the substituents R ^{1 to} R ⁴ is an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms, more preferably carbon. 1 to 6 atoms, more preferably 1 to 3 carbon atoms, particularly preferably methyl or ethyl. The alkyl group may have a substituent.
In the present specification, the “alkyl group” may be linear, branched or cyclic, but is preferably a linear alkyl group.

In the general formula (1), when one or more of the substituents R ^{1 to} R ⁴ is an aralkyl group, the aralkyl group preferably has 7 to 15 carbon atoms, more preferably carbon. It has 7 to 10 atoms. The aralkyl group may have a substituent. Examples of the aralkyl group include benzyl and phenethyl.

In the general formula (1), when one or more of the substituents R ^{1 to} R ⁴ are a heterocyclic group, the heterocyclic group is preferably a 3- to 8-membered ring, and 5 or 6 More preferably, it is a member ring. Examples of the ring-constituting hetero atom of the heterocyclic group include one or more of a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic group may have a substituent. Examples of the heterocyclic group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, pyrrolidyl, morpholino, piperidino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like.

In the general formula (1), when one or more of the substituents R ^{1 to} R ⁴ is an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably carbon. It has 6 to 10 atoms. The aryl group may have a substituent. As the aryl group, phenyl, alkylphenyl group, trifluoromethylphenyl, alkoxyphenyl group, chlorophenyl group, nitrophenyl group, and cyanophenyl group are preferable, and phenyl, trifluoromethylphenyl, and methoxyphenyl are more preferable.

In the general formula (1), the substituents R ^{1 to} R ⁴ are more preferably any one of the following (A) to (D).
(A) An embodiment in which all of R ^{1 to} R ⁴ are alkyl groups.
(B) R ¹ and R ² are alkyl groups, and either one of R ³ and R ⁴ is a hydrogen atom and the other is an aryl group, either one is alkyl, and the other is both an aryl group Some aspects.
(C) An embodiment in which ^one of R ¹ and R ² is a hydrogen atom, the other is an aryl group, or both are aryl groups, and R ³ and R ⁴ are alkyl groups.
(D) R ¹ and R ² are connected to each other to form a heterocyclic group containing at least a nitrogen atom to which R ¹ and R ² are bonded as a ring-constituting hetero atom in the general formula (1), and / or An embodiment in which R ³ and R ⁴ are connected to each other to form a heterocyclic group containing at least a nitrogen atom to which R ³ and R ⁴ are bonded in the general formula (1) as a ring-constituting heteroatom.
Examples of the heterocyclic group in the embodiment (D) include morpholino, piperidino, pyrrolidino and the like, more preferably piperidino and morpholino.

-Substituents R ⁵ and R ^6-
In the above general formula (1), the substituents represented by R ⁵ and R ⁶ are amino groups, alkyl groups, alkoxy groups, aralkyl groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, halogen atoms, acyl groups. , Carbamoyl group, amide group, sulfinyl group, phosphini group and the like.

The alkyl group, alkoxy group and alkylthio group preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. In the present specification, the “alkoxy group” may be either linear or branched, but is preferably linear.
The aralkyl group preferably has 7 to 15 carbon atoms, more preferably 7 to 10 carbon atoms.
The aryl group, aryloxy group and arylthio group preferably have 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
The above exemplified substituents may have a substituent.

At least one of the substituents represented by R ⁵ and R ⁶ is preferably an alkyl group, and more preferably both are alkyl groups. The alkyl group is more preferably methyl or ethyl, and even more preferably methyl.

M and n representing the numbers of R ⁵ and R ⁶ are preferably integers of 0 to 2, and more preferably 0 or 1.

-Substituent R ^7-
In the general formula (1), the substituent R ⁷ is a group having a group having a carbonyl group or a sulfonyl group, and more preferably a group connected to a nitrogen atom via a carbonyl group or a sulfonyl group.
Examples of when R ⁷ has a carbonyl group include an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an N-substituted carbamoyl group, a heterylcarbonyl group, and the like. These groups may have a substituent.
Examples of when R ⁷ has a sulfonyl group include an alkylsulfonyl group, an arylsulfonyl group, an N-substituted sulfamoyl group, a heterylsulfonyl group, and the like. These groups may have a substituent.
The alkoxy group or alkyl group in the alkoxycarbonyl group, alkylcarbonyl group, or alkylsulfonyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and further preferably 1 to 3. preferable. Further, the aryl group and arylene group in the arylcarbonyl group and arylsulfonyl group preferably have 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
Among these, R ⁷ is preferably an alkylcarbonyl group, an alkylsulfonyl group, an arylcarbonyl group, or an arylsulfonyl group, and more preferably acetyl, benzoyl, chlorophenylcarbonyl, or phenylsulfonylphenylenecarbonyl.

The substituent R ⁷ is detached from the mother nucleus by intramolecular cleavage following one-electron oxidation by light irradiation. Thereafter, it is presumed that color development is caused by air oxidation of the mother nucleus after desorption.

—Substituent R ⁸ —
R ⁸ in the general formula (1) is a hydrogen atom, an alkyl group or an aryl group. The alkyl group and aryl group may have a substituent. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, and particularly preferably methyl or ethyl. In addition, examples of the aryl group include phenyl, alkylphenyl group, alkoxyphenyl group and the like, and among them, phenyl or methoxyphenyl is preferable.

  The azine compound represented by the general formula (1) is preferably a compound represented by the following general formula (2a) or the following general formula (2b).

In the general formula (2a), R ⁵ , R ⁶ , R ⁷ , m and n have the same meanings as described in the general formula (1), and preferred embodiments thereof are also described in the general formula (1). Is the same.
In the general formula ^{(2a), R} 11 ~R ¹⁴ represents a hydrogen atom, an alkyl group or an aryl group. R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may combine with each other to form a heterocyclic ring containing at least a nitrogen atom as a ring constituent atom. In addition, the heterocyclic ring may have an unsaturated bond.
In the general formula (2a), Y represents an oxygen atom or a sulfur atom.
Hereinafter, the general formula (2a) will be described more specifically.

-Substituents R ¹¹ , R ¹² , R ¹³ and R ^14-
In the general formula (2a), when one or more of the substituents R ^{11 to} R ¹⁴ is an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms, more preferably carbon. 1 to 6 atoms, more preferably 1 to 3 carbon atoms, particularly preferably methyl, ethyl and n-propyl. The alkyl group may have a substituent.

In the general formula (2a), when one or more of the substituents R ^{11 to} R ¹⁴ is an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably carbon. It has 6 to 10 atoms. The aryl group may have a substituent. The aryl group is preferably a phenyl, alkylphenyl group, trifluoromethylphenyl, or alkoxyphenyl group, and more preferably phenyl, trifluoromethylphenyl, or methoxyphenyl.

In the general formula (2a), R ^{11 to} R ¹⁴ are more preferably any one of the following (E) to (H).
(E) An embodiment in which all of R ^{11 to} R ¹⁴ are alkyl groups.
(F) An embodiment in which R ¹¹ and R ¹² are alkyl groups, and one of R ¹³ and R ¹⁴ is a hydrogen atom, the other is an aryl group, or both are aryl groups.
(G) An embodiment in which either one of R ¹¹ and R ¹² is a hydrogen atom, the other is an aryl group, or both are aryl groups, and R ¹³ and R ¹⁴ are alkyl groups.
(H) R ¹¹ and R ¹² are connected to each other to form a heterocyclic group containing at least a nitrogen atom to which R ¹¹ and R ¹² are bonded in the general formula (2a) as a ring-forming hetero atom, and / or linked R ¹³ and R ¹⁴ together, the general formula (2a) in at R ¹³ and R ¹⁴ embodiment is formed including at least heterocyclic group with the nitrogen atom to which they are attached as a ring-constituting heteroatom.
Examples of the heterocyclic group in the embodiment (H) include morpholino, piperidino, pyrrolidino, and the like, and piperidino and morpholino are more preferable.

In the general formula (2b), R ⁵ , R ⁶ , R ⁷ , m and n have the same meanings as described in the general formula (1), and preferred embodiments thereof are also described in the general formula (1). Is the same.

In the general formula ^{(2b), R} 21 ~R ²⁴ represents a hydrogen atom, an alkyl group or an aryl group. R ²¹ and R ²² , R ²³ and R ²⁴ may be bonded to each other to form a heterocyclic ring containing at least a nitrogen atom as a ring constituent atom. In addition, the heterocyclic ring may have an unsaturated bond.
In the general formula (2b), R ²⁸ represents a hydrogen atom, an alkyl group or an aryl group.

-Substituents R ²¹ , R ²² , R ²³ and R ^24-
In the general formula (2b), when one or more of R ^{21 to} R ²⁴ is an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms, more preferably the number of carbon atoms. 1 to 6, more preferably 1 to 3 carbon atoms. The alkyl group may have a substituent.

In the general formula (2b), when one or more of the substituents R ^{21 to} R ²⁴ is an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably carbon. It has 6 to 10 atoms. The aryl group may have a substituent.
The aryl group is preferably phenyl, alkylphenyl group, trifluoromethylphenyl, alkoxyphenyl group or chlorophenyl, more preferably phenyl, trifluoromethylphenyl or methoxyphenyl.

In the general formula (2b), R ^{21 to} R ²⁴ are more preferably any one of the following (I) to (L).
(I) An embodiment in which R ²¹ and R ²² are alkyl groups, one of R ²³ and R ²⁴ is a hydrogen atom, and the other is an aryl group.
(J) An embodiment in which any one of R ²¹ and R ²² is a hydrogen atom, the other is an aryl group, and R ²³ and R ²⁴ are alkyl groups.
(K) An embodiment in which one of R ²¹ and R ²² is a hydrogen atom, the other is an aryl group, one of R ²³ and R ²⁴ is a hydrogen atom, and the other is an aryl group.
(L) R ²¹ and R ²² are connected to each other to form a heterocyclic group containing at least a nitrogen atom to which R ²¹ and R ²² are bonded in general formula (2b) as a ring-constituting heteroatom, and / or An embodiment in which R ²³ and R ²⁴ are connected to each other to form a heterocyclic group containing at least a nitrogen atom as a ring-forming hetero atom.
In the embodiment (L), examples of the heterocyclic group include morpholino, piperidino, pyrrolidino, and the like, and piperidino and morpholino are more preferable.

(Azine compound content)
In the color former of the present invention, the content of the azine compound is preferably 0.01 to 50% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 0.05 to 10% by mass in the total solid content. %.

Specific examples of the azine-based compound contained in the color former of the present invention are illustrated below.
In the following exemplary compounds, Ph represents a phenyl group, and Me represents a methyl group.

(Photopolymerizable monomer, photopolymerization initiator)
The color former of the present invention preferably contains a photopolymerizable monomer and a photopolymerization initiator. If a color former containing these components is applied onto a substrate and irradiated with light of a specific wavelength for initiating the polymerization reaction, a stronger and more stable color development cured film can be formed on the substrate. Can do. The hardness and flexibility of the color-forming cured film can be appropriately controlled by adjusting the amount of the photopolymerizable monomer used and the number of polymerizable functional groups in the photopolymerizable monomer.

Examples of the photopolymerizable monomer that can be contained in the color former of the present invention include 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) Acrylate, (meth) acrylic acid esters such as bisphenol fluorene type epoxy di (meth) acrylate, although dimethylacrylamide (DMA) and the like are exemplified, but not limited thereto. The amount of the photopolymerizable monomer is preferably 50 to 99.9% by mass, more preferably 70 to 99.9% by mass, based on the solid content of the color former.
The (meth) acrylate is used as a concept including both acrylate and methacrylate.

  Although there is no restriction | limiting in particular in the photoinitiator which can be contained in the color former of this invention, It is preferable that it is an initiator which has absorption in 365 nm or 405 nm. Examples of such photopolymerization initiators include benzophenone photopolymerization initiators, acetophenone photopolymerization initiators, benzoin photopolymerization initiators, benzoin ether photopolymerization initiators, thioxanthone photopolymerization initiators, and anthraquinone photopolymerization initiators. Examples thereof include one or more selected from a polymerization initiator, a naphthoquinone photopolymerization initiator, a triazine photopolymerization initiator, and an oxime photopolymerization initiator. The content thereof is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 1 to 5% by mass in the color former. Further, the content in the solid content of the color former is 0.01 to 10% by mass, more preferably 0.01 to 7% by mass, and particularly preferably 0.05 to 5% by mass.

(Coloring aid)
In the present invention, in order to further improve the color developability, a color aid is preferably used. As the color developing aid, an initiator having a high absorption at 365 nm or less and a low absorption at 365 nm or more among photopolymerization initiators can be used. For example, acetophenone series and onium salt series are mentioned.
Specifically, for example, Irg. 907, Irg. 184, Irg. 2959, Irg. 250, DARUCURE 1173, CYRACURE UVI-6990 (all are trade names), diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, and the like.
The amount used is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 1 to 5% by mass in the color former. The content of the color former in the solid content is 0.01 to 50% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 0.05 to 10% by mass.

(Other components of the color former of the present invention)
The color former of the present invention may contain a solvent, a binder, and the like as the balance in addition to the azine compound, the photopolymerizable monomer, the photopolymerization initiator, and the color development aid.
Solvents that can be used include, but are not limited to, propylene glycol methyl ether acetate, t-amyl alcohol, methanol, isopropanol, water, ethyl ethyl ketone, ethyl acetate and the like. The amount of the solvent is preferably 0.1 to 80% by mass, more preferably 1 to 50% by mass in the color former.
As the binder, various resins can be used. For example, a polyester resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, or a blend resin of two or more of these can be used. The content of the binder is preferably 0 to 99.9% by mass, and more preferably 40 to 95% by mass in the solid content of the color former.

(Manufacture of azine compounds)
The azine compound of the present invention can be synthesized by a conventional method. In that case, for example, Journal of the Chemical Society, Perkin Transactions 1, 1983, 2111. WO 2010/111534, pages 121-123, Can. J. et al. Chem. VOL. , 54, 1976, 2909, JP 2009-196955 A, and the like can be referred to.

[Coloring film of the present invention, image forming method]
In the color forming film or image forming method using the color former of the present invention, the azine compound develops color when irradiated with light. When the color former contains a photopolymerizable monomer, the polymerization reaction is allowed to proceed by irradiating light with a wavelength or intensity at which the azine-based compound is difficult to develop a color, and then a curable compound film is formed. A desired color-developing film or image can be formed by irradiating light having a wavelength or intensity capable of inducing color development.

The conditions of the color forming film and the image forming method will be described.
1) Wavelength When the color former of the present invention contains a photopolymerizable monomer, the polymerization treatment irradiation light for polymerization is preferably at a wavelength of 365 nm or more, more preferably at a wavelength of 365 nm or 405 nm, particularly preferably A wavelength of 365 nm is used.
The color treatment is not particularly limited in wavelength, and may be all colors, but preferably includes a wavelength of less than 365 nm.
2) Energy amount of irradiation light The polymerization is preferably 0.001 J / cm ^{2 to 20} J / cm ^2, more preferably 0.01 J / cm ^{2 to} 15 J / cm ^{2, and} particularly preferably 0.1 J / cm ^{2 to} 10 J / cm ^{2. 2} .
The color reaction, preferably more preferably ^1J / cm ^{2 ~4500J} / cm 2 and particularly preferably ^1J / cm ^{2 ~1500J} / cm 2 was ^{1J / cm 2 ~100J / cm 2} , most preferably 1 J / ^cm 2 ~ 50 J / cm ² .

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. In the following examples, “part” means “part by mass” unless otherwise specified.

[Synthesis example]
Specific compound example A1 was synthesized by the following route.

Journal of Medicinal Chemistry, 2007, Vol. 50, 2281. 100 mg of compound (1) synthesized with reference to was dissolved in 15 ml of water, and then 15 ml of CHCl ₃ was added. Next, a solution prepared by dissolving 0.1 g of NaOH, 0.82 g of NaHCO ₃ and 0.26 g of Na ₂ S ₂ O ₄ in 10 ml of water was added thereto with stirring. After the color of the aqueous layer changed from black to yellow, a solution of PhCOCl 1 ml in CHCl ₃ was added dropwise with stirring. After completion of the dropping, the CHCl ₃ layer was distilled off under reduced pressure. The obtained residue was separated by silica gel column chromatography, and the obtained crystal was dried to obtain 21 mg of compound (A1).

  Other compounds (A2, A3, A5, A9) were synthesized in the same manner.

The results of subjecting synthesized compounds A1, A2, A3, A5, and A9 to TOF-mass analysis are shown below.
A1: m / z 390 (M + H)
A2: m / z 374 (M + H)
A3: m / z 438 (M + H)
A5: m / z 436 (M + H)
A9: m / z 681 (M + H)

  Moreover, the following compounds P1 and P2, which are existing color forming compounds, were prepared as color developing reference compounds.

[Test Example 1]
1 part of compound A1, 100 parts of HEMA, photopolymerization initiator Irg. 1 part of 819, 48 parts of PGMEA (propylene glycol methyl ether acetate) and 0.75 part of EGDMA (ethylene glycol dimethacrylate) were mixed and applied to the glass with a spin coater. Thereafter, it was cured by irradiation with light having a wavelength of 365 nm or more and 405 nm or less (100 mW) for about 20 seconds.
Thereafter, irradiation with light of all wavelengths (200 to 600 nm, 100 mW) was performed for about 5 minutes to develop the entire cured film.
The resulting color film was visually observed for color and color developability (degree of coloring of the cured film). The color developability was evaluated according to the following evaluation criteria.

<Evaluation criteria for color development>
A: Fairly colored B: Firstly colored C: Less colored The stronger the coloring, the better the color development and the more preferable.

Moreover, it replaced with compound A1 and conducted the same test using compound A2, A3, A5, A9, P1, and P2.
The results are shown in Table 1 below.

[Test Example 2]
1 part of compound A1, 100 parts of MMA, 1 part of color developing aid diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, photopolymerization initiator Irg. 1 part of 819, 47 parts of PGMEA and 0.75 part of EGDMA were mixed and applied to the glass with a spin coater. Thereafter, it was cured by irradiation with light having a wavelength of 365 nm or more and 405 nm or less (100 mW) for about 20 seconds. Thereafter, as in Test Example 1, the entire cured film was colored by irradiation with light of all wavelengths (100 mW) for about 5 minutes.
About the obtained color development film, the color of the color development and the color developability were evaluated in the same manner as in Test Example 1. Also, instead of the compound A1, the same test was performed using the compounds A2, A3, A5, A9, P1 and P2. went.
The results are shown in Table 2 below.

  As shown in the results of Tables 1 and 2, the azine-based compounds defined in the present invention had the physical property of coloring black when irradiated with light. And it was shown that the color former of the present invention containing this azine compound is excellent in black color developability by light irradiation and is suitable for forming a black color development film and a black image.

Claims (12)

A color former containing an azine compound represented by the following general formula (1) as a color developing component.

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, a heterocyclic group or an aryl group. R ⁵ and R ⁶ each independently represent a substituent. X represents an oxygen atom, Represents a sulfur atom or NR ⁸ , R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents a group having a carbonyl group or a sulfonyl group, and m and n each independently represents an integer of 0 to 3. .) The color former according to claim 1, wherein the azine-based compound is represented by the following general formula (2a).

(In the formula, R ⁵ , R ⁶ , R ⁷ , m and n are as defined in the general formula (1). R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. Y represents Represents an oxygen atom or a sulfur atom.) The color former according to claim 1, wherein the azine-based compound is represented by the following general formula (2b).

(In formula, R < ⁵ >, R < ⁶ >, R < ⁷ >, m, and n are synonymous with the said General formula (1). R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, or an aryl group each independently. R < ²⁸ >. Represents a hydrogen atom, an alkyl group or an aryl group.)   The color former according to any one of claims 1 to 3, which develops a black color.   The color former according to any one of claims 1 to 4, which develops color when irradiated with light.   The color former according to any one of claims 1 to 5, comprising a color former.   The color former according to any one of claims 1 to 6, comprising a photopolymerizable monomer and a photopolymerization initiator.   The color former according to any one of claims 1 to 7, which is used for image formation.   A method for forming a color developing film or an image, comprising: a step of forming a film using the color former according to any one of claims 1 to 8; and a step of irradiating the film with all light to cause color development. An azine compound represented by the following general formula (1).

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, a heterocyclic group or an aryl group. R ⁵ and R ⁶ each independently represent a substituent. X represents an oxygen atom, Represents a sulfur atom or NR ⁸ , R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, R ⁷ represents a group having a carbonyl group or a sulfonyl group, and m and n each independently represents an integer of 0 to 3. .) The azine compound according to claim 10, which is represented by the following general formula (2a).

(In the formula, R ⁵ , R ⁶ , R ⁷ , m and n are as defined in the general formula (1). R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. Y represents Represents an oxygen atom or a sulfur atom.) The azine compound according to claim 10, which is represented by the following general formula (2b).

(In formula, R < ⁵ >, R < ⁶ >, R < ⁷ >, m, and n are synonymous with the said General formula (1). R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, or an aryl group each independently. R < ²⁸ >. Represents a hydrogen atom, an alkyl group or an aryl group.)