JP2000103166A - Image-recording material and image-recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image-recording material in which the preservability and coloring properties of a coloring agent are compatibilized with each other, and the discoloration at the preservation time of the formed color image is improved. SOLUTION: An image recording material containing a compound represented by the formula is heated into the image form to form an image. In the formula, Ar represents aryl or an aromatic heterocyclic group. D represents a group other than acyl group separated by heat or acid. L represents a group to be separated after removal of D. R1 and R2 and C together represent a coloring matter-forming coupler residue, and C represents a coupling carbon. R1 and R2 may be bonded to form a ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel image forming material. More specifically, the present invention relates to a novel color image forming material, and more particularly to a color image forming material which can be applied to formation of a visible image of a dry film for color hard copy, color proof, graphic art, and the like.

[0002]

2. Description of the Related Art Various dry image forming methods have been proposed, and most of them are color forming methods utilizing an equilibrium system of acid and base. These methods have a problem that the color varies depending on the environment in which the light-sensitive material is placed, and have been continuously improved.

On the other hand, there have been proposed some irreversible color developing methods as a means for drastically improving this. JP-A-57-46239 proposes a method in which a color is formed by cutting a sulfonyl group with light.
U.S. Pat. No. 3,409,457 proposes a method in which an acylamino group is cleaved by heating and an alkali in the system to form an azomethine dye. U.S. Pat. No. 4,720,449 and JP-A-5-148426.
The di-color, which is colored by the cleavage of the acyl group by an intramolecular reaction,
Alternatively, a triarylmethane dye or an indoaniline dye has been proposed. Further US Pat.
602,263 and 5,243,052 propose a system in which a carbonate group derived from a tertiary alcohol is cleaved by heat to produce a dye. However, in both cases, the compatibility between the preservability of the color former and the color developability was insufficient, and its improvement was required.

Japanese Patent Application Laid-Open No. 8-292517 proposes a system in which a color is formed by an intramolecular reaction utilizing heat and a subsequent reaction. In this case, too, both the preservability of the color former and the color developability are required. It was not enough.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method and an image forming medium in which a color change during storage of a formed color image is greatly improved. Another object of the present invention is to provide an image forming method and an image forming medium in which the balance between the preservability of the color former and the color developability is improved.

[0006]

The object of the present invention has been solved by the following method. An image recording material comprising a compound represented by the following general formula (1).

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(In the formula (1), Ar represents an aryl group or an aromatic heterocyclic group. D represents a group other than an acyl group which is released by heat or an acid. L represents a group which is released after D is released. R ¹ and R ² and C together represent a dye-forming coupler residue, and C represents a coupling carbon.
¹ and R ² may combine to form a ring. The image recording material as described in the general formula (1), wherein R ¹ and R ² are combined to form a ring.

An image forming method comprising forming an image by heating an image recording material containing the compound represented by the general formula (1) imagewise. An image forming method as described in the above item, comprising a compound absorbing a laser beam and a compound represented by the general formula (1), and irradiating with the laser to imagewise heat.

An image recording material comprising a compound which generates an acid by light or heat and a compound represented by the general formula (1). An image forming method comprising irradiating a laser to a recording material containing a compound generating an acid by light and a compound represented by the general formula (1) to form an image.

A compound which generates an acid by heat and a general formula
An image forming method, wherein an image is formed by heating a recording material containing the compound represented by (1). An image as described above, comprising a compound that absorbs laser light, a compound that generates an acid by heat, and a compound represented by the general formula (1), and is heated imagewise by irradiating the laser. Forming method.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. In the general formula (1), R ¹ , R ² and C together represent a dye-forming coupler residue, and C represents a coupling carbon. R ¹ and R ² may combine to form a ring. R ¹
As the dye-forming coupler residue consisting of R ² and C, various base nuclei known in the photographic industry can be used. Specific examples of these couplers (mother nuclei) include Theory of the Photographic Process (4th. Ed.
H. James ed., Macmillan, 1977) pp. 291-334 and 354-361, JP-A-58-12353, 58.
No. 149046, No. 58-149047, No. 59-
Nos. 11114, 59-124399, 59-17
No. 4835, No. 59-231439, No. 59-231
No. 540, No. 60-2951, No. 60-14242
And Nos. 60-23474 and 60-66249.

Examples of the coupler nucleus preferably used in the present invention are listed below. The couplers preferably used in the present invention include the following general formulas (C-1) to (C-1).
There is a structure as described in 2). These are active methylene, pyrazolone, pyrazoloazole,
Residues of couplers collectively referred to as phenol, naphthol, and pyrrolotriazole, which are known in the art.

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Formulas (C-1) to (C-4) each represent a residue of a coupler referred to as an active methylene coupler, wherein R ²¹ represents an optionally substituted acyl group, cyano group or cyano group. Group, nitro group, aryl group, heterocyclic residue, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group or arylsulfonyl group.

In the general formulas (C-1) to (C-3),
R ²² is an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (C-4), R ²³ is an aryl group or a heterocyclic residue which may have a substituent.

Examples of the substituent which R ²¹ , R ²² and R ²³ may have include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl, methyl, Ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, chain or cyclic having 2 to 50 carbon atoms An alkenyl group (eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), an alkynyl group having 2 to 50 carbon atoms (eg, ethynyl, 1-propynyl, etc.), an aryl group having 6 to 50 carbon atoms (eg, , Phenyl, naphthyl, anthryl, etc.), an acyloxy group having 1 to 50 carbon atoms (eg, acetoxy, tetradecanoyloxy) Benzoyloxy),

A carbamoyloxy group having 1 to 50 carbon atoms (for example, N, N-dimethylcarbamoyloxy and the like);
A carbonamide group having 1 to 50 carbon atoms (for example, formamide, N-methylacetamide, acetamido, N-methylformamide, benzamide, etc.);
Sulfonamide groups (eg, methanesulfonamide,
Dodecane sulfonamide, benzene sulfonamide, p
Carbamoyl group having 1 to 50 carbon atoms (for example, N-methylcarbamoyl, N, N
-Diethylcarbamoyl, N-mesylcarbamoyl, etc.) and a sulfamoyl group having 0 to 50 carbon atoms (for example, N
-Butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl and the like, an alkoxy group having 1 to 50 carbon atoms (for example, methoxy, propoxy, isopropoxy, octyl) Oxy, t-octyloxy, dodecyloxy, 2-
(2,4-di-t-pentylphenoxy) ethoxy and the like), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, naphthoxy and the like),
An aryloxycarbonyl group having 7 to 50 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl A hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl),

An alkylthio group having 1 to 50 carbon atoms (eg, methylthio, octylthio, cyclohexylthio, etc.), an arylthio group having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.), a ureido group having 1 to 50 carbon atoms (eg, , 3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide, etc.), having 2 carbon atoms
To 50 heterocyclic groups (for example, nitrogen,
A 3- to 12-membered monocyclic or condensed ring containing at least one or more, preferably 1 to 9, oxygen and sulfur, such as 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, -Imidazolyl, morpholino, 2
-Quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), having 1 to 50 carbon atoms
(E.g., acetyl, benzoyl, trifluoroacetyl, etc.) and a sulfamoylamino group having 0 to 50 carbon atoms (e.g., N-butylsulfamoylamino, N
-Phenylsulfamoylamino, etc.), having 3 to 50 carbon atoms
(E.g., trimethylsilyl, dimethyl-t
-Butylsilyl, triphenylsilyl and the like), and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

In the general formulas (C-1) to (C-4),
R ²¹ and R ²² , and R ²¹ and R ²³ may combine with each other to form a ring.

The formula (C-5) represents a residue of a coupler called a 5-pyrazolone coupler, wherein R ²⁴ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group. R ²⁵ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.

Among the residues represented by formula (C-5), those in which R ²⁴ is an aryl group or an acyl group and R ²⁵ is a phenyl group substituted by one or more halogen atoms are preferred.

More specifically, R ²⁴ is a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5- (3-octadecenyl) group. -1-succinimide) phenyl group, 2-chloro-5-
Octadecylsulfonamidophenyl group, 2-chloro-
An aryl group such as a 5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group,
Or an acetyl group, a 2- (2,4-di-t-pentylphenoxy) butanoyl group, a benzoyl group, a 3- (2,4
Acyl groups such as -di-t-amylphenoxyacetamido) benzoyl group, and these groups may further have a substituent, and these may be an organic substituent linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Group or a halogen atom.

R ²⁵ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group.

The general formula (C-6) represents a residue of a coupler called a pyrazoloazole coupler, wherein R ²⁶ represents a hydrogen atom or a substituent. Q ¹ represents 2 to 4 nitrogen atoms.
Represents a group of non-metallic atoms necessary for forming a 5-membered azole ring, and the azole ring may have a substituent (including a condensed ring).

Among the pyrazoloazole couplers represented by the general formula (C-6), US Pat. No. 4,500,63
No. 0, the imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,654.
5-b] -1,2,4-triazoles, pyrazolo [5,1-c] described in U.S. Pat. No. 3,725,067.
-1,2,4-Triazoles are preferred.

For details of the substituents on the azole ring represented by the substituents R ²⁶ and Q ¹ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 22279, which is a residue of a pyrazolotriazole coupler having a carboxamide group in the molecule.

Formulas (C-7) and (C-8) are the residues of couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁷ is a hydrogen atom, -C
_{^{ONR 29 R 30, -SO 2 NR}} 29 R 30, -NHCOR 29,
It represents a -NHCONR ²⁹ R ³⁰ or -NHSO ₂ NR ²⁹ R ^30. Here, R ²⁹ and R ³⁰ represent a hydrogen atom or a substituent. In the general formulas (C-7) and (C-8), R ²⁸ represents a substituent, l is an integer selected from 0 to 2, and m is 0 to 4
Represents an integer selected from When l and m are 2 or more, R ²⁸
May be different from each other. Examples of the substituent of R ^{28 to} R ³⁰ include those described as examples of the substituent of R ^{21 to} R ²³ .

Preferred examples of the residue of the phenolic coupler represented by formula (C-7) include US Pat. Nos. 2,369,929, 2,801,171, and 2,772. No. 162, No. 2,895,826,
2-Acylamino-5-alkylphenols described in U.S. Pat. No. 3,772,002 and the like; U.S. Pat.
No. 162, No. 3,758,308, No. 4,12
No. 6,396, No. 4,334,011, No. 4,3
No. 27,173, West German Patent Publication No. 3,329,729
2,5-diacylaminophenols described in U.S. Pat. No. 3,446,6
No. 22, No. 4,333,999, No. 4,451,
Residues of 2-phenylureido-5-acylaminophenol-based couplers described in, for example, No. 559 and No. 4,427,767 can be exemplified.

Preferred examples of the residue of the naphthol coupler represented by the formula (C-8) include US Pat. Nos. 2,474,293, 4,052,212 and 4,146. No. 396, No. 4,282,233,
2-carbamoyl-1-naphthol described in U.S. Pat. No. 4,296,200 and the like and U.S. Pat. No. 4,690,88.
Residues of 2-carbamoyl-5-amide-1-naphthol couplers described in No. 9 and the like can be mentioned.

Formulas (C-9) to (C-12) are pyrrolo.
A residue of a coupler called a triazole,³¹,
R³²And R³³Represents a hydrogen atom or a substituent, respectively.
You. R ³¹, R³²Or R³³As the substituent represented by
R^{twenty one}~ R^{twenty three}Examples of the substituents include those mentioned above.
You. Pyrrolo represented by general formulas (C-9) to (C-12)
Preferred examples of triazole-based coupler residues include
State Patent Nos. 488,248A1 and 491,197A
R described in No. 1 and No. 545,300³¹And R ³²of
Coupler residues in which at least one is an electron-withdrawing group
I can do it.

Others include coupler residues having a structure such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle. it can.

As the residue of the fused phenol coupler, US Pat. Nos. 4,327,173 and 4,564,5
Nos. 86 and 4,904,575, and the like.

As the residue of the imidazole coupler,
U.S. Pat. Nos. 4,818,672 and 5,051,3
No. 47 and the like can be used.

As the residue of the 3-hydroxypyridine-based coupler, the residue of a coupler described in JP-A-1-315736 can be used.

The active methylene and active methine coupler residues are described in US Pat. Nos. 5,104,783 and 5,104,783.
162, 196 and the like can be used.

Examples of the residue of the 5,5-condensed heterocyclic coupler include pyrrolopyrazole couplers described in US Pat. No. 5,164,289 and pyrroleimidazole couplers described in JP-A-4-174429. Can be used.

Examples of the residue of the 5,6-fused heterocyclic coupler include pyrazolopyrimidine couplers described in US Pat. No. 4,950,585, and pyrrolotriazine couplers described in JP-A-4-204730. , European Patent No. 55
Residues such as couplers described in 6,700 can be used.

In addition to these coupler residues, German Patent Nos. 3,819,051A and 3,823,049,
U.S. Pat. Nos. 4,840,883 and 5,024,9
No. 30, No. 5,051,347, No. 4,481,
No. 268, European Patent Nos. 304,856A2 and 32
No. 9,036, No. 354, 549A2, No. 37
No. 4,781A2, No. 379,110A2, No. 3
86,930A1, JP-A-63-141055, JP-A-64-32260, JP-A-64-32261, JP-A-2
No. -297475, No. 2-44340, No. 2-110
555, 3-7938, 3-160440,
Nos. 3-172839, 4-172247, 4-
No. 179949, No. 4-182645, No. 4-184
Nos. 437, 4-188138, 4-188139
Nos. 4,194,847, 4,204,532, 4-204731, and 4-204732 can also be used.

In the general formula (1), L represents a group which leaves after D is removed. Examples of L include a heterocyclic group (a saturated or unsaturated 5- to 7-membered monocyclic or condensed ring containing at least one of nitrogen, oxygen, sulfur and the like as a hetero atom. As succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4
-Triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole,
Imidazoline-2,4-dione, oxazolidine-2,
4-dione, thiazolidine-2,4-dione / imidazolidine-2-one, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazoline-2- On, 2-pyrrolin-5-one, 2-imidazoline-5
On, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-
3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4
-Thiazolidine-4-one, etc.),

A halogen atom (eg, chlorine atom, bromine atom, etc.), an aryloxy group (eg, phenoxy, 1-
Naphthoxy, etc.), a heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.), an alkoxy group (eg, methoxy, dodecyloxy, etc.), a carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (eg,
Methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxadiazoli) Ruthio, benzimidazolylthio, etc.), alkylthio groups (eg, methylthio, octylthio, hexadecylthio, etc.),

An alkylsulfonyloxy group (eg, methanesulfonyloxy), an arylsulfonyloxy group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), a carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide Groups (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl groups (eg, methanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.), alkylsulfinyl groups (eg, methanesulfinyl, etc.), arylsulfinyl groups (Eg, benzenesulfinyl); an arylazo group (eg, phenylazo, naphthylazo); a carbamoylamino group (eg, N-methylcarbamoylamino).

L may be substituted by a substituent,
Examples of the substituent that substitutes L include R ^{twenty one}~ R^{twenty three}With a substituent of
Those mentioned are mentioned.

L is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group.

In the general formula (1), D is a group that can be cleaved by heat or an acid, and represents a group other than an acyl group. Specifically -CO ₂ -R ^{41 _{group, -C (R 43) 2 -O}} -R 42 group, -
C (R ⁴³ ) ₂ —S—R ⁴² group, —C (R ⁴³ ) ₂ —N (R ⁴² )
₂ group, -Si (R ⁴³⁾ ₃ group, -P (= O) (R 44) 2 group, -P
^{(= S) (R 44)} 2 group, -SO ₂ R ⁴³ group, -C (= O) N
(R ^{4 5)} represents a ₂ group or the like. Here, the R ⁴¹ group is a secondary or tertiary alkyl group (for example, t-butyl, sec-butyl, 1,1,1,2).
3,3-tetramethylbutyl, 2-phenyl-2-propyl, etc.). The R ⁴² group is an alkyl group (eg, methyl,
Represents an octyl, dodecyl, t-butyl, sec-butyl, etc.), an aryl group (eg, phenyl, naphthyl, etc.), or a heterocyclic group (eg, pyridyl, pyrazolyl, etc.). R ⁴³
Represents an alkyl group or an aryl group (specific examples include R ⁴²
The same as those exemplified above). R ⁴⁴ is an alkyl group, an aryl group, -OR ⁴³ group, -N (R ⁴³⁾ represents a ₂ group or -SR ⁴³ group (the specific examples are the same as those exemplified in R ^42, R ^43). R
⁴⁵ represents a hydrogen atom, an alkyl group or an aryl group (the specific examples are the same as those exemplified in R ^42). When a plurality of groups represented by R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ are present in a molecule, they may be the same or different. Further, the groups represented by R ^{41 to} R ⁴⁵ may further have a substituent, and specific examples thereof include those described as the substituents of R ^{21 to} R ²³ . Specific examples of D are shown below, but the present invention is not limited thereto.

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In the general formula (1), Ar represents an aryl group or an aromatic heterocyclic group. These groups may further have a substituent, and examples of the substituent include the aforementioned R ^{21 to} R ²³
There are those listed above. When Ar represents an aryl group (for example, phenyl or naphthyl), -N in the general formula (1)
The (D)-group preferably has an amino group or a hydroxyl group at the p-position. When Ar represents an aromatic heterocyclic group, the ring size is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring. Specific examples thereof include furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, Pyridazine, indole, pyrazole, triazole, quinoxaline, benzisothiazole and the like.

Ar is preferably —N in the general formula (1).
The p-position of the (D)-group is an aryl group substituted with an amino group or a hydroxyl group, and more preferably the p-position of the -N (D)-group in the general formula (1) is an amino group or a hydroxyl group. Is a phenyl group substituted with In the compound represented by the general formula (1) of the present invention, some molecules may be bonded to form an oligomer or a polymer. At that time, a copolymer may be formed with an acid generator or another monomer described below.

Hereinafter, specific examples of the compound represented by the general formula (1) of the present invention will be shown, but the present invention is not limited thereto.

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The compounds of the present invention can be synthesized by various methods. Although various synthetic routes can be considered as typical synthetic routes, as shown below, a two-equivalent coupler in the photographic industry and a developing agent having a substituent D in the general formula (1) of the present invention are used as an oxidizing agent. Is the most convenient route in many cases.

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The synthesis examples of the exemplified compounds of the present invention are shown below. (Synthesis Example) Synthesis of Exemplified Compound (1)

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Compound (1-a) (10 mmol) and compound (1-a)
b) 10 mmol was dissolved in 50 ml of methylene chloride, and 20 mmol of the compound (1-d) was added thereto. Subsequently, compound (1)
-D) 10 mmol was added, and the mixture was stirred at room temperature for 2 hours. Thereafter, 100 ml of water and 100 ml of ethyl acetate were added to the reaction solution and stirred, and the aqueous layer was separated. The organic layer was further washed with water and brine, and then concentrated. The residue was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 1 /
2), Exemplified compound (1) was obtained in a yield of 38%.

As an image forming method using the compound of the present invention, there is a method of applying heat imagewise. Heating methods include contacting with a heated block or plate, contacting with a heat roller or heat drum, irradiating a halogen lamp or infrared or far-infrared lamp heater, or forming an image with a thermal head of a thermal printer. There are a heating method, a method of irradiating a laser beam, and the like. When the recording material of the present invention is used for a material requiring a high resolution, such as a plate making material, a method of scanning and exposing with a laser beam is preferable. In order to form an image with less heat energy, the recording material can be pre-warmed to an appropriate temperature.

When an image is formed by irradiating a laser beam, a dye that absorbs light of the wavelength of the laser beam must be present in order to convert the laser beam into heat energy. Excimer laser, argon laser, helium neon laser, semiconductor laser, glass (YAG) laser, carbon dioxide laser,
Although there is a dye laser and the like, a helium neon laser, a semiconductor laser and a glass laser are laser light sources useful in the present invention. Among them, a semiconductor laser is particularly useful because the device is small and inexpensive. The oscillation wavelength of a semiconductor laser is usually 670 to 830 nm, and a dye having absorption in the near infrared is used. As the near-infrared absorbing dye, a cyanine dye, a squarylium dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, and the like are used. As a specific example, for example, US Pat.
No. 973,572, No. 4,948,777, No. 4,950,640, No. 4,950,639, No. 4,948,776, No. 4,948,778, No. No. 4,942,141, No. 4,952,552, No. 5,036,040 and No. 4,912,083
And the like.

When a compound that generates an acid by light is used, a laser is selected according to the absorption characteristics of the photoacid generator. At this time, various dyes may be added for the purpose of spectral sensitization, but in that case, it is necessary to select a laser according to the absorption wavelength of the dye. The compounds of the present invention also develop color upon reaction with an acid. Examples of the image forming method at that time include a method in which an acid is generated imagewise by light or heat to form an image. As such an acid generating method and an acid generating agent, “Organic Materials for Imaging” edited by Organic Electronics Materials Research Group (Bunshin Publishing, 19
1993) and JP-A-4-212962.

Specific examples of the onium salt type include phosphonium salts and sulfonium salts (for example, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, triphenylsulfonium tetrafluoroborate, diphenyl (4-chlorophenyl) sulfonium Tetrafluoroborate, diphenyltolylsulfonium tetrafluoroborate, tris (4-methoxyphenyl) hexafluoroantimonate, iodonium salt (for example, diphenyliodonium tetrafluoroborate, (4-octyloxyphenyl) phenyliodonium hexafluorophosphate, (4 -Octyloxyphenyl)
Phenyliodonium hexafluoroantimonate,
Bis (N-dodecylphenyl) iodonium hexafluoroantimonate), and the like. Specific examples other than the onium salts include those described in the above-mentioned references.

Other acid generators include Journal
of American Chemical Society, Volume 120, p. 37 (1998
), The method described in WO94-10607, and the like. Specific examples of the compounds belonging to these are shown below, but the present invention is not limited thereto.

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[0074]

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In the case of a photoacid generator, various sensitizers (J. Polymer, Sci., 16, 2441 (1978)
Can be used.

In the present invention, a small amount of a base is added for the purpose of enhancing the storage stability of the image recording medium, and a compound capable of generating an acid by the action of light or heat is separately added for the purpose of enhancing the sensitivity. Various additives such as a pigment, an antioxidant, and an anti-sticking agent can be added according to the requirements. Further, an overcoat layer may be provided to protect the image recording layer, or a backcoat layer may be provided on the back surface of the support. Various known techniques for heat-sensitive recording materials can be used, such as providing a single layer or a plurality of undercoat layers made of pigment or resin between the image recording layer and the support.

When a base is added, an organic base is preferable. For example, guanidine derivatives (for example, 1,3-diphenylguanidine, 1,3-dimethylguanidine, 1,3-
Dibutylguanidine, 1-benzylguanidine, 1,
1,3,3-tetramethylguanidine, etc.), aniline derivatives (eg, aniline, pt-butylaniline, N,
N′-dimethylaniline, N, N′-dibutylaniline, triphenylamine, etc.), alkylamine derivatives (eg, tributylamine, octylamine, laurylamine, benzylamine, dibenzylamine, etc.), and heterocyclic compounds (eg, N , N'-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-
Undecene, triphenylimidazole, lutidine, 2
-Picoline and the like) are preferred examples. These bases are 1 to 5 based on the composition represented by A in the general formula (1).
It is preferable to add 0 mol%, particularly preferably 5 to 2
This is the case where 0 mol% is added.

When a pigment is added, examples include diatomaceous earth, talc, kaolin, calcined kaolin, titanium oxide, silicon oxide, magnesium carbonate, calcium carbonate, aluminum hydroxide, and urea-formalin resin.

Other additives include UV absorbers such as benzophenone type and benzotriazole type, head wear and sticking preventives comprising higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin, paraffin oxide, polyethylene, Waxes, such as polyethylene oxide and caster wax, are mentioned, and can be added as needed.

As the support used in the image recording medium of the present invention, papers such as high quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,
6-naphthylene dicarboxylate, polyarylene,
Examples thereof include polymer films such as polyimide, polycarbonate, and triacetyl cellulose, glass, metal foil, and nonwoven fabric. In the case where the image recording medium of the present invention is used for a transmission type image such as an OHP film or a plate making film, a transparent support is used. For a plate making film, a support having a small coefficient of thermal expansion and good dimensional stability and having no absorption in the photosensitive region of the PS plate is selected.

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The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 <Preparation of Sample> 2 mmol of the compound of the present invention and 0.85 g of polystyrene (polystyrene beads manufactured by Wako Pure Chemical Industries, diameter: about 3.2 mm, average 3000-mer) were dissolved in chloroform.
A transparent recording sheet (sample 101) was prepared by applying the composition on a 100 μm-thick polyethylene terephthalate film at a rate of 2 mmol / m ² and drying. Similarly, sample 10
2-105 were created. As a comparative sample, a film coated with Reference Sample 106 in the same manner was prepared.

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<Heat Development> The film was sandwiched between glass plates and heated on a heat block at 200 ° C. for 15 seconds. The color development rate was calculated from the dye concentration when the same coating amount was separately applied.

<Evaluation of Storage Property>
The storage stability was evaluated by performing forced thermolysis for 7 days at 70 ° C./humidity and calculating the decomposition rate from the color density. The results are shown in Table 1. As is clear from Table 1,
The compounds of the present invention are compatible with each other in terms of color development and storage stability, and the usefulness of the present invention was apparent.

[0090]

[Table 1]

Example 2 <Preparation of Sample> 2 mmol of the compound of the present invention, 0.85 g of polystyrene (polystyrene beads manufactured by Wako Pure Chemical Industries, diameter: about 3.2 mm, average 3000-mer), infrared absorbing dye (IR-
1) 35 mg was dissolved in chloroform, coated on a 100 μm-thick polyethylene terephthalate film at 2 mmol / m ² , dried and dried to form a transparent recording sheet (sample 20).
1) was created. Samples 202 to 203 were prepared in the same manner.

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<Image formation by laser> (Laser exposure conditions for image recording) Spectra Diode
Labs No.SDL-2430 (wavelength range: 800-830nm)
This multiplexing was performed to obtain an output of 400 mW to obtain an image writing laser. Using this laser, beam system 160
μm, laser scanning speed 0.5 m / sec (center of scanning), sample feed speed 15 mm / sec, scanning pitch 8 lines / mm.
Exposure was performed so that an image of 2 mm × 9 mm was obtained. At this time, the laser energy density on the sample was 5 mJ / mm ² . The color development rate was calculated from the dye concentration of a film separately coated with the same coating amount. The results are shown in Table 2.

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[Table 2]

As is evident from Table 2, the compounds of the present invention show good coloring properties even in a coloring system using a laser.

Example 3 <Preparation of sample> 2 mmol of the compound of the present invention, 0.85 g of polystyrene (polystyrene beads, manufactured by Wako Pure Chemical Industries, diameter: about 3.2 mm, average 3000-mer), 4 mm of exemplified compound A- (4)
ol was dissolved in chloroform, applied to a 100 μm-thick polyethylene terephthalate film at a concentration of 2 mmol / m ² , and dried to prepare a transparent recording sheet (sample 301). Samples 302 to 303 were prepared in the same manner. <Heat development> The film was sandwiched between glass plates and heated on a heat block at 180 ° C for 15 seconds. The color development rate was determined by extracting the contents from the film and quantifying the amount of the formed pigment. Table 3 shows the results.

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[Table 3]

As is evident from Table 3, the presence of the acid generator makes it possible to produce the same color even at a lower temperature than in Example 1.

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According to the image recording material of the present invention, the color change during storage of the formed color image is greatly improved. Further, according to the present invention, compatibility between the storage stability of the color former and the color developability is improved.

Claims (8)

[Claims] 1. An image recording material comprising a compound represented by the following general formula (1). Embedded image (In the formula (1), Ar represents an aryl group or an aromatic heterocyclic group. D represents a group other than an acyl group which is released by heat or an acid. L represents a group which is released after D is removed. R
¹ and R ² and C together represent a dye-forming coupler residue, and C represents a coupling carbon. R ¹ and R ² may combine to form a ring. ) 2. The image recording material according to claim ¹ , wherein, in the general formula (1), R ¹ and R ² are combined to form a ring. 3. An image forming method, wherein an image is formed by heating an image recording material containing the compound represented by the general formula (1) according to claim 1 in an imagewise manner. 4. A compound absorbing a laser beam and a compound represented by the general formula:
4. The image forming method according to claim 3, wherein the image is heated by irradiating the laser with the compound represented by the formula (1). 5. An image recording material comprising a compound capable of generating an acid by light or heat and a compound represented by the general formula (1) according to claim 1. 6. A compound capable of generating an acid by light and a compound according to claim 1.
An image forming method, comprising irradiating a recording material containing the compound represented by the above general formula (1) with a laser to form an image. 7. A compound capable of generating an acid by heat and a compound according to claim 1.
An image forming method, wherein an image is formed by heating a recording material containing the compound represented by the general formula (1) described above. 8. A composition comprising a compound that absorbs laser light, a compound that generates an acid by heat, and a compound represented by the general formula (1), and is heated imagewise by irradiating the laser. The image forming method according to claim 7, wherein