JPH10158253A - Naphthooxadinine squarylium compound and recording material containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound applicable as a dye in a photosensitive material and a light-heat conversion dye in a thermal recording material. SOLUTION: A naphtooxadinine squarylium compound of the formula [R<1> to R<6> are each H, an alkyl, a cycloalkyl, an aryl, a heterocyclic group, an aralkyl, etc.; R<7> and R<8> are each H or a monovalent group; (n) is an integer of 1-3]. This compound can be used as an antihalation dye, an irradiation dye, etc., in a recording material, e.g. a halogenated silver-based photosensitive material or a heat developing photosensitive material. When it is used, the compound is preferably added in a form of a solution dissolved in an organic solvent. The quantity of the addition of the compound is preferably 0.1-1000mg/m<2> , and if a binder is used, the compound is added at a ratio of 0.1-60wt.% based on the binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel naphthooxazinin squarylium compound and a recording material containing the same.
In particular, the present invention relates to a photothermographic material, a silver halide photographic material, and a heat-sensitive recording material.

[0002]

2. Description of the Related Art Naphthoxazinine compounds are known as CAN.J.CH
EM. VOL51. 1981-1989 (1973), but no squarylium compound using it is known. On the other hand, various compounds are known as dyes for preventing halation and irradiation of photographic light-sensitive materials (including heat-developable light-sensitive materials). In particular, for a recording material sensitized to an infrared wavelength, for example, a photographic photosensitive material (including a heat-developable photosensitive material) as a recording material for recording with the output of a near-infrared laser, halation absorbing in the infrared region of the spectrum. Anti- and anti-irradiation dyes are needed. US5,38
No. 0,635 uses a dihydroperimidine squarylium dye, but has a problem in that the sharpness is poor when a 780 nm laser is used. Further, it was found that when used as a printing light-sensitive material, absorption at 350 to 450 nm was large. Further, in Japanese Patent Application No. 8-167416, a dihydroperimidine squarylium dye is used as a dye for photothermal conversion, but it has been found that there is a problem in the residual ratio of the dye.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel naphthoxazinine squarylium compound, and furthermore, a photographic material (including a photothermographic material) and a light / photosensitive material containing the same as a dye. An object of the present invention is to provide a heat-sensitive recording material containing the dye as a heat conversion dye.

[0004]

Means for Solving the Problems The object of the present invention has been achieved by a naphthooxazinin squarylium compound represented by the following general formula (1).

[0005]

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[0006] In the ^{formula, R 1, R 2, R} 3, R 4, R 5 and R ⁶ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or aralkyl group, R ¹ And R ² and / or R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered ring. R ⁷ and R ⁸ represent a hydrogen atom or a monovalent group.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail. In the general formula (1), the alkyl group represented by R ¹ to R ⁶ is an alkyl group having 1 to 20, more preferably 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, butyl, hexyl, undecyl) It is. Further, halogen atoms (F, Cl, Br), alkoxycarbonyl (for example, methoxycarbonyl, ethoxycarbonyl), hydroxy, alkoxy (for example, methoxy, ethoxy, phenoxy, isobutoxy), sulfo (or salt), carboxyl (or salt) Good) or acyloxy (eg, acetyloxy, butyryloxy, hexylyloxy, benzoyloxy) and the like. R
Examples of the cycloalkyl group represented by ¹ to R ⁶ include cyclopentyl and cyclohexyl. The aryl group represented by R ¹ to R ⁶ preferably has 6 to 12 carbon atoms and includes a phenyl group or a naphthyl group. The aryl group may be substituted. Examples of the substituent include an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, butyl), an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy), and an aryloxy group (eg, phenoxy, p- Chlorophenoxy), halogen atom (F, Cl, Br), alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl), cyano group, nitro group, amino group (eg, methylamino, acetylamino, methanesulfonamide), sulfo group (Which may be a salt) and a carboxyl group (which may be a salt). The aralkyl group represented by R ¹ to R ⁶ is preferably an aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenylethyl) and has a substituent (eg, methyl, methoxy, chloro atom). You may. Examples of the heterocyclic group represented by R ¹ to R ⁶ include thienyl, furyl, pyrrolyl, pyrazolyl, pyridyl, indolyl and the like. R ³ and R ⁶ are preferably a hydrogen atom. 1 represented by R ⁷ and R ⁸
Examples of the valent group include the substituents described above for the aryl group. R ¹ and R ² , or R ⁴ and R ⁵ may combine with each other to form a cyclopentane or cyclohexane ring.
The bonding position of the squarin ring is usually in the ortho position to the amino group, but may be in the para position in some cases. The ortho position is preferred. Specific examples of the present invention are shown below.

[0008]

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[0009]

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[0010]

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The compound of the present invention can be used as a recording material, for example, as an antihalation or irradiation dye in a silver halide light-sensitive material or a heat-developable light-sensitive material. Or as a filter for near-infrared light, or as a dye for light / heat conversion. It can also be used for pharmaceutical or diagnostic applications. The compound is preferably dissolved in an organic solvent and added. Compounds, 0.1~1000mg / m ^2, may preferably 1 to 200 mg / m ² is added. When using a binder, 0.1 to 60% by weight of the binder,
Preferably 0.2 to 30% by weight, more preferably 0.5%
-10% by weight.

It is preferable that the photothermographic material is substantially left on the image sheet where the compound is observed, because of its easiness on the earth. More preferably, it is a mono-sheet type (a type in which all materials provided for forming an image are completed as an image sheet to be observed) and a photothermographic material. Further, in order to achieve the object, a photothermographic material for infrared laser exposure is preferably used. Further, the wavelength of the infrared laser exposure is preferably 750 nm or more.

The photothermographic material of the present invention forms a photographic image using a photothermographic processing method. As such a photothermographic material, for example, US Pat. No. 3,152,904
No. 3457075 and D.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials) Neblette No. 8
Edition, Sturge, V. Walworth
th), A. Edited by Shepp, page 2, 1969
Year).

The photothermographic material of the present invention may be any as long as it can form a photographic image by using a heat development process. The photothermographic material has a reducible silver source (eg, organic silver salt) and a catalytically active photocatalyst (eg, halogen). It is preferable that the photothermographic material contains a color tone controlling agent for controlling the color tone of silver and a reducing agent, usually in a state dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature,
After exposure, development is performed by heating to a high temperature (for example, 80 ° C. or higher). Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter layer may be formed on the same side or the opposite side as the photosensitive layer, or a dye represented by the general formula (1) of the present invention may be formed on the photosensitive layer. Other dyes or pigments may be included. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

The support applicable to the photothermographic material of the present invention includes, for example, paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth and the like;
Sheets or films of metals such as aluminum, copper, magnesium, zinc; glass or chromium alloy, steel,
Glass coated with a metal such as silver, gold, platinum; poly (alkyl methacrylates) (eg, poly (methyl methacrylate)), poly (esters) (eg, poly (ethylene terephthalate)), poly (vinyl acetal) ), Poly (amides) (eg, nylon), and cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate). The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

The respective binder layers (for example, synthetic polymers) together with the chemicals in the photothermographic material of the present invention may form a self-supporting film. The support is made of known auxiliary materials, for example, vinylidene chloride, acrylic acid monomers (for example, acrylonitrile and methyl acrylate)
And copolymers and terpolymers of unsaturated dicarboxylic acids (eg, itaconic acid, acrylic acid), carboxymethylcellulose, poly (acrylamide); and similar polymeric materials.

Suitable binders are transparent or translucent, generally colorless, natural polymer synthetic resins and polymers and copolymers, and other film-forming media, such as:
Gelatin, gum arabic, poly (vinyl alcohol),
Hydroxyethyl cellulose, cellulose acetate,
Cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are described in Research Disclosure No. 1702.
No. 9, including the following: imides (eg, phthalimide); cyclic imides, pyrazoline-5
-Ones and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides (for example, N-hydroxy-1, 8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,
2,4-triazole); N- (aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium derivatives and certain photobleaches. Combinations (e.g., N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate), and 2-
(Tribromomethylsulfonyl) benzothiazole combinations); merocyanine dyes (e.g., 3-ethyl-
5-((3-ethyl-2-benzothiazolinylidene (be
nzothiazolinylidene)) -1-Methylethylidene) -2
-Thio-2,4-oxazolidinedione (oxazolidined
ione)); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (eg, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro- 1,4-
Phthalazine dione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine +
Combination of phthalic acid; phthalazine (including phthalazine adduct) and maleic anhydride, and phthalic acid, 2,3
-Combination with at least one compound selected from naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazoline Diones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (eg,
2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (for example, 3,6-dimerocapto-1,
4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene. A preferred toning agent is phthalazine:

[0020]

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## EQU1 ## The reducing agent may contain a so-called photographic developer, for example, phenidone, hydroquinones, catechol and the like, but hindered phenol is preferred. A color light-sensitive material as disclosed in U.S. Pat. No. 4,460,681 is also conceivable for realizing the present invention.

Examples of suitable reducing agents are described in US Pat.
Nos. 448, 3773512, 3959633, and Research Disclosure Nos. 17029 and 29.
963, and include: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, Piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (for example, Np-
Methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfohydroxamic acids (eg, benzenesulfohydroxamic acid); sulfonamidoanilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Amidooxins; Azines (for example, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids; Azines and sulfone Combinations of amidophenols; α-cyanophenylacetic acid derivatives; bis-β-naphthol and 1,3-
5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (e.g., 2,6-dimethoxy-3) , 5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-
Hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4 -Ethylidene-bis (2
-T-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Preferred developers are hindered phenols of the general formula (A):

[0023]

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Wherein R ⁴⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, —C ₄ H ₉ , 2, 4,
R ⁴¹ and R ⁴² are an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl,
t-butyl).

Silver halide useful as a catalytically active amount of photocatalyst can be any photosensitive silver halide (eg, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, chloroiodobromide). Silver or the like), but preferably contains iodine ions. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. The content of silver halide is 0.6 to 0.03 g / m ² , more preferably,
0.4 to 0.05 g / m ² . Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

The reducible silver source can be any material containing a reducible silver ion source. Silver salts of organic and heteroorganic acids, especially long chains (10-30, preferably 15-25
) Aliphatic carboxylic acids are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are described in Research Disclosure No. 1702.
9 and 29996, and include the following:
Salts of organic acids (eg, gallic acid, oxalic acid, behenic acid,
Stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); aldehyde Silver complexes (e.g., aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-
Dihydroxybenzoic acid, 5,5-thiodisalicylic acid),
Silver salts or complexes of thioenes (eg, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole ,
Urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-
Complexes or salts of silver and nitrogen acids selected from triazoles and benzotriazoles; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. The preferred silver source is silver behenate. The reducible silver source preferably has a silver content of 3 g / m ² or less and 0.1 g / m ² or more. More preferably, 2 g / m ² or less, 0.1 g / m ²
m ² or more.

Such a photosensitive material may contain an antifoggant. The most effective antifoggant was mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 03. However, mercury compounds are environmentally unfriendly. As the non-mercury antifoggant, for example, antifoggants such as those disclosed in U.S. Pat. Nos. 4,460,075 and 4,452,885 and JP-A-59-57234 are preferable.

Particularly preferred non-mercury antifoggants are compounds such as those disclosed in US Pat. Nos. 3,874,946 and 4,756,999, —C (X ¹ ) (X ² ) (X ³ ), where X ¹ and X ² Is a heterocyclic compound having one or more substituents represented by halogen (eg, F, Cl, Br and I) and X ³ is hydrogen or halogen. Examples of suitable antifoggants include:

[0029]

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[0030]

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Even more suitable antifoggants are disclosed in US Pat. No. 5,028,523 and our UK patent application No. 92221.
Nos. 383.4, 9300147.7, 931179
No. 0.1.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651 and JP-A-6-259561.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used.

In the field of photothermographic material printing, an image forming system exhibiting ultra-high contrast photographic characteristics has been provided in order to improve the reproduction of continuous tone images or the reproduction of line images by halftone images. Thus, a super-high contrast agent can be used for forming a super-high contrast image. For example, U.S. Patent Nos. 5,464,738, 5,496,695, 6,512,411, 5,536,622, and Japanese Patent Application Nos. 7-228627 and 8-215822.
Nos. 8-130842, 8-148113, 8-156378, 8-148111, 8-1
The hydrazine derivative described in No. 48116, the compound having a quaternary nitrogen atom described in Japanese Patent Application No. 8-83566, and the acrylonitrile compound described in US Pat. No. 5,545,515 can be used. Specific examples of the compound include the aforementioned US Pat. No. 5,464,73.
Compounds 1 to 10 of No. 8 and H- of No. 5,496,695
1 to H-28, I-1 to I of Japanese Patent Application No. 8-215822.
-86, H-1 to H-62 of JP-A-8-130842, 1-1 to 1-21 of JP-A-8-148113, 8-148
No. 1 to 50 of No. 111 and Nos. 1 to 4 of No. 8-148116
0, P-1 to P-26 of JP-A-8-83566, and T
-1 to T-18, C in U.S. Pat. No. 5,545,515.
N-1 to CN-13 and the like. Further, in the present invention, for forming a super-high contrast image, a high contrast enhancement agent can be used in combination with the above-mentioned super-high contrast agent. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically AM-1 to AM-5, and hydroxamic acids described in 5,545,507, specifically HA-1 to AM-5 HA-1
1, acrylonitriles described in 5,545,507, specifically CN-1 to CN-13, 5,558,
No. 983, specifically, CA-
1 to CA-6, onium salts described in Japanese Patent Application No. 8-132636, specifically A-1 to A-42, B
-1 to B-27, C-1 to C-14 and the like can be used. The synthesis method, addition method, addition amount, and the like of these super-high contrast agents and high-contrast accelerators can be performed as described in each of the cited patents.

The super-high contrast agents used in the present invention include:
Any of the above super-high contrast agents may be used as long as they have the performance to achieve the object of the present invention, but hydrazine derivatives are preferably used. As the hydrazine derivative used in the present invention, the following hydrazine derivatives are preferably used. (In some cases, they can be used in combination.) The hydrazine derivative used in the present invention can be synthesized by various methods described in the following patents.

(Formula 1) described in JP-B-6-77138
And specifically the compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication
Compounds 1 to 38 on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4─1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formulas (1) and (2) described in JP-A-6-289520, specifically from page 5 to
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by general formula (H) and general formula (Ha) described in JP-A-7-104426, specifically, compound H described on pages 8 to 15 of the same publication
-1 to H-44. JP-A-9-22082, which is a compound characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. , A compound represented by the general formula (B), the general formula (C), the general formula (D), the general formula (E), or the general formula (F), specifically, the compound N-1 described in the same publication. To N-30. JP-A-9-
No. 22082, compounds represented by the general formula (1), specifically, compounds D-1 to D-5 described in the publication
5.

Further, from pages 25 to 3 of “Known Techniques (pages 1 to 207)” (published on March 22, 1991) (published by Aztec).
Various hydrazine derivatives described on page 4. JP-A-62-8
Compounds D-2 and D-3 of No. 6354 (pages 6 to 7)
9. The hydrazine nucleating agent of the present invention is a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, the powder of the hydrazine derivative can be dispersed in a suitable solvent by a ball mill, a colloid mill, a Manton-Gauling, a microfluidizer, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or any other layer. It is preferable to add it to the layer adjacent thereto. The addition amount of the nucleating agent of the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, and more preferably 1 × 10 ⁻⁵ mol.
５5 × 10 ^-3 mol is more preferable, and 2 × 10 ^-5 -5 × 1
0 ^-3 mol and most preferred.

The compounds of the present invention can be used in silver halide photosensitive materials. Regarding spectral sensitizers and silver halide emulsions used for silver halide photosensitive materials,
JP-A-6-43583 can be referred to. When the compound of the present invention is used for a heat-sensitive recording material, the method described in Japanese Patent Application No. 8-167416 can be referred to.

[0039]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention. Example 1 (Synthesis) (Synthesis of Compound 2) 8-amino-1-naphthol 6.3
g and 20 ml of ethyl alcohol in 5-undecanone.
1 g was added and refluxed for 9 hours. Further, 15 g of 5-undecanone was added, and the mixture was refluxed for 3 hours. The reaction product was concentrated and purified by column chromatography (silica gel, n-hexane / ethyl acetate = 1/5) to give naphthooxazinine 2.6.
g was obtained. 2.6 g of the naphthooxazinin obtained above,
0.5 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione, 30 ml of n-butanol and 30 parts of toluene
The mixture was reacted at an external temperature of 140 ° C. for 3 hours while expelling generated water. The reaction product was concentrated and purified by column chromatography (silica gel, chloroform) to obtain 0.6 g of Compound 2. λmax: 781.3 nm (CHCl ₃ ), ε = 1.69 × 10 ⁵ Melting point: 193-5 ° C. Other compounds can be synthesized in the same manner. Table 1 shows λmax and melting point of the synthesized compounds.

[0040]

[Table 1]

[0041] Example 2 (the photothermographic material) a light-sensitive emulsion A mixed solution NaOH 89 g Distilled water 1500ml solution of concentrated HNO ₃ 19 ml distilled water 50ml solution prepared solution stearate 131g behenic acid 635g of distilled water 13 liters 85 ° C. 15 minutes AgNO ₃ 365 g Distilled water 2500 ml solution Polyvinyl butyral 86 g Ethyl acetate 4300 ml solution Polyvinyl butyral 290 g Isopropanol 3580 ml Solution N-bromosuccinimide 17 g Acetone 690 ml

While maintaining the temperature of the solution at 85 ° C., the solution was added over 5 minutes while stirring vigorously.
Add over 5 minutes. After stirring for 20 minutes as it is, 35
Cool down to ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes.
Thereafter, the solution was added, the stirring was stopped, and the mixture was left to stand. The aqueous phase was removed together with the contained salt to obtain an oil phase. The solvent was removed to remove traces of water. Then, the solution was added and the mixture was stirred vigorously at 50 ° C. Thereafter, the solution was added over 20 minutes and stirred for 105 minutes to obtain Emulsion A.

The following layers were sequentially formed on a polyethylene terephthalate support colored blue with Dye-A. Drying was performed at 75 ° C. for 5 minutes each.

[0044]

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Back side coating Antihalation layer (wet thickness 80 microns) 1: 1 mixture of polyvinyl butyral (10% isopropanol solution) and cellulose acetate butyrate (10% isopropanol solution) 150 ml dye (use acetone as solvent) 70mg

[0046]

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Photosensitive layer side coating Photosensitive layer (wet thickness 140 μm) Photosensitive emulsion A 73 g Sensitizing dye-1 (0.1% DMF solution) 2 ml Antifoggant-1 (0.01% methanol solution) 3 ml Fog Inhibitor-2 (0.85% methanol solution) 10 ml Antifoggant-3 (0.85% methanol solution) 10 ml Phthalazone (4.5% DMF solution) 8 ml Reducing agent-1 (10% acetone solution) 13 ml dye ( The solvent used is acetone, DMF or methylene chloride.

[0048]

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Surface protective layer (wet thickness 100 microns) acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 0.72 g tetrachlorophthalic acid 0.22 g tetrachlorophthalic anhydride 0.5g

[0050]

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Sensitometry The photothermographic material prepared above is processed into a half-cut size,
A 780 nm laser diode was exposed with a beam tilted 13 ° from the vertical. Then use a heat drum for 1
Heat development was performed at 20 ° C for 5 seconds. Evaluation of Sharpness Exposure to white light of 2856K was performed using light separated using an interference filter of 780 nm, processed under the above conditions, and sharpness was determined using an MTF value of 15 lines / mm at an optical density of 1.0. evaluated.

Evaluation of color The samples that had been heat-developed without exposure were visually evaluated. ○: good △: worried about color ×: poor color

[0053]

[Table 2]

Table 2 shows that the sample of the present invention has no residual color and has no problem in color. Also, the sharpness is good.

Example 3 (Photothermographic Material) Preparation of Photosensitive Emulsion B Solution 131 g of stearic acid 635 g of behenic acid Distilled water 13 liters 85 ° C. for 15 minutes Solution A Cubic AgBrI prepared in advance (I = 4 mol%) 0.06μ (0.14 mol as Ag) distilled water 1250ml solution NaOH 89g distilled water 1500ml solution concentrated HNO ₃ 19ml distilled water 50ml solution AgNO ₃ 365g distilled water 2500ml solution polyvinyl butyral 86g ethyl acetate 4300ml solution polyvinyl butyral 290g 8035

While maintaining the temperature of the solution at 85 ° C., the solution A is added over 10 minutes with vigorous stirring, the solution is added over 5 minutes, and then the solution is added over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes. Thereafter, the solution was added, the stirring was stopped and the mixture was left to stand, and the aqueous phase was extracted together with the salt contained therein to obtain an oil phase. After removing the traces of water by removing the solvent, the solution was added and the mixture was stirred vigorously at 50 ° C. Later, 10
Emulsion B was obtained by stirring for 5 minutes.

A test was conducted in the same manner as in Example 2 except that the antihalation layer was provided below the photosensitive layer on the side of the photosensitive layer. As in Example 2, the sample using the dye of the present invention had no residual color, good color, and high sharpness.

Example 4 (Silver halide photosensitive material) Preparation of silver halide emulsion 34 g of gelatin was dissolved in 850 ml of H ₂ O, and 1.7 g of sodium chloride, 0.1 g of potassium bromide and the following compound (A) were placed in a vessel heated to 65 ° C.

[0059]

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After adding 70 mg, 500 ml of an aqueous solution containing 170 g of silver nitrate and hexachloroiridium having a molar ratio of iridium to the finished silver halide of 5 × 10 ^-7.
(III) Potassium (III) and 500 ml of an aqueous solution containing 12 g of sodium chloride and 98 g of potassium bromide were added by a double jet method to prepare cubic monodispersed silver chlorobromide particles having an average particle size of 0.35 μm. After desalting the emulsion, 50 g of gelatin was added, and the pH was 6.5 and the pAg was
After adding 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid in accordance with 8.1 and performing chemical sensitization at 65 ° C., 4-hydroxy-6-methyl-1,3,3a, 7-tetrazain 0.2 g of den was added and the mixture was quenched and solidified (emulsion A). Next, 0.3 μm cubic monodispersed silver chlorobromide particles were prepared in the same manner as in Emulsion A except that the gelatin solution was heated to 40 ° C., and after desalting, 50 g of gelatin was added.
5, adjusted to pAg 8.1. To this emulsion were added 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid, and after chemical sensitization at 65 ° C, 4-hydroxy-6-methyl-1,3,3a,
Emulsion B was prepared by adding 0.2 g of 7-tetrazaindene and rapidly cooling and solidifying.

[0061] 2. Preparation of Emulsion Coating Solution Emulsions (A) and (B) were mixed at a weight ratio of 1: 1 and the following additives were added per mol of silver halide to prepare an emulsion coating solution.

(Formulation of Emulsion Coating Solution) Spectral sensitizing dye [2] 1.0 × 10 ^-4 mol b. Supersensitizer [3] 0.7 × 10 ^-3 mol c. Preservability improver [4] 1 × 10 ^-3 mol d. Polyacrylamide (molecular weight 40,000) 7.5 g e. Dextran 7.5 g f. Trimethylolpropane 1.6 g g. Polystyrene sulfonate Na 1.2 g h. Poly (ethyl acrylate / methacrylic acid) latex 12 g N, N'-ethylenebis- (vinylsulfoneacetamide) 3.0 g 1-phenyl-5-mercapto-tetrazole 50 mg

Spectral sensitizing dye [2]

[0064]

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Supersensitizer [3]

[0066]

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Preservability improver [4]

[0068]

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3. Preparation of coating solution for emulsion layer surface protective layer

The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution.

(Formulation of Coating Solution for Surface Protective Layer of Emulsion Layer)

B. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12 g c. Sodium polystyrene sulfonate (molecular weight: 600,000) 0.6 g d. N, N'-ethylenebis- (vinylsulfoneacetamide) 2.2 g e. 2.7 g of polymethyl methacrylate fine particles (average particle size: 2.0 μm) Sodium t-octylphenoxyethoxyethanesulfonate 1.8 g g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0 g Ji. Sodium polyacrylate 6.0 g C ₈ F ₁₇ SO ₃ K 70 mg nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70 mg Le. NaOH (1N) 6 ml III. 90 ml of methanol. Compound [5a] 0.06 g

[0073]

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4. Preparation of Back Layer Coating Solution The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a back layer coating solution. However, the dye of the present invention was dissolved in the compound (6a), and emulsified and dispersed using a surfactant in an appropriate amount by a conventional method.

[0075]

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(Formulation of Coating Solution for Back Layer) Gelatin 100 g b. Dye [listed in Table 3] 4.2 g c. 1.2 g of sodium polystyrene sulfonate d. Poly (ethyl acrylate / methacrylic acid) latex 5 g e. N, N'-ethylenebis- (vinylsulfoneacetamide) 4.8 g f. Compound [5a] 0.06 g g. Dye [B] 0.3 g h. Dye [C] 0.05 g Colloidal silica 15 g

Dye [B]

[0078]

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Dye [C]

[0080]

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5. Preparation of Coating Solution for Back Surface Protective Layer The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a coating solution. (Formulation of coating solution for back surface protective layer)

B. Gelatin 100 g b. 0.5 g of sodium polystyrene sulfonate c. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.9 g d. Polymethyl methacrylate fine particles (average particle size: 4.0 μm) 4 g e. Sodium t-octylphenoxyethoxyethanesulfonate 2.0 g f. NaOH (1N) 6 ml g. Sodium polyacrylate 2.4 g h. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 4.0 g C ₈ F ₁₇ SO ₃ K 70 mg nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70 mg Le. Methanol 150 ml III. Compound [5a] 0.06 g

6. Creating photographic materials

The above-mentioned coating solution for the back layer was coated together with the coating solution for the surface protective layer of the back layer on the side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3 g / m ² . Subsequently, the emulsion coating solution and the surface protective layer coating solution described above were coated on the opposite side of the support with a coating Ag amount of 2.3 g / m ^2.
And the amount of gelatin applied to the surface protective layer was 1 g / m ² (Photographic Material 1).

The photographic materials 1 to 4 were kept at 25 ° C. and 60% temperature and humidity for 7 days after coating, exposed in the same manner as in the sensitometry of Example 2, and were subjected to the following using a roller transport type automatic developing machine. Development processing was carried out using a developing solution [I] and a fixing solution [I]. The development time is 7 seconds, the fixing time is 7 seconds, the rinsing time is 4 seconds, and the draining and drying time is 11 seconds. At this time, the transfer speed is 300
mm / min.

Developer [I] Composition

Potassium hydroxide 29 g Sodium sulfite 31 g Potassium sulfite 44 g Ethylenetriaminetetraacetic acid 1.7 g Boric acid 1 g Hydroquinone 30 g Diethylene glycol 29 g 1-Phenyl-3-pyrazolidone 1.5 g Glutaraldehyde 4.9 g 5-Methylbenzotriazole 60 mg 5-nitroindazole 0.25 g Potassium bromide 7.9 g Acetic acid 18 g upto 1000 ml pH 10.3 Fixing solution [I] composition

Ammonium thiosulfate 140 g Sodium sulfite 15 g Disodium ethylenediaminetetraacetate disodium salt 20 mg Sodium hydroxide 7 g Aluminum sulfate 10 g Boric acid 10 g Sulfuric acid 3.9 g Acetic acid 15 g Up to 1000 ml with H ₂ O pH 4.30 Evaluation of sharpness and color was performed in the same manner as in Example 2. However, development was performed by the above-mentioned development method. Table 3 shows the obtained results.

[0089]

[Table 3]

From the results shown in Table 3, the dye of the present invention has no residual color and has no problem in color. Also, the sharpness is good.

Example 5 The following compounds were dissolved in methyl ethyl ketone to prepare a colored composition solution, applied to a 100 μm-thick polyethylene terephthalate film, and dried to produce a colored transparent sheet. Polyvinyl butyral is manufactured by Monsanto Butva
r ^TM B76 was used. Preparation of sample Polyvinyl butyral 0.85 g / m ² Leuco dye 1 mmol / m ² Acid 3 mmol / m ² Dye (described in Table 4) 0.13 mg / m ²

[0092]

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[0093]

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<Exposure conditions for image formation> Spectra Di
ode Labs No. SDL-2430 (wavelength range: 800-8)
(30 nm) were combined to produce an output of 800 mW, which was used as an image writing laser. Using this laser, a beam diameter of 160 μm and a laser scanning speed of 0.5 m /
Exposure was performed on the above-described sample so that an image of 22 mm × 9 mm was formed with the sample (scanning central portion), the sample feeding speed set at 15 mm / sec, and the scanning pitch set at 8 lines / mm. At this time, the laser energy density on the sample was 10 mJ / mm ² . The energy density was changed as shown in Table 4 by changing the laser scanning speed and the laser output. <Evaluation of Dye Residual Rate at Laser Scanning Center (Image Area)>
The minimum density (Dmin) of the laser scanning center portion (image portion) was determined by Macbeth blue light or green light density measurement, and the dye remaining ratio was evaluated from the ratio to the non-image portion. Table 4 shows the obtained results.

[0095]

[Table 4]

From Table 4, it was found that the dye of the present invention has a low residual dye ratio.

Example 6 (Heat-developable photosensitive material) (Preparation of silver halide particles A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, and the pH was adjusted to 3.0 at a temperature of 35 ° C. After, 74g of silver nitrate
370 ml of an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 94: 6 and containing K ₃ [IrCl ₆ ].
While maintaining Ag 7.7, it was added over 10 minutes by the control double jet method. [IrCl ₆ ] ^-3 was added at 3 × 10 ^-7 mol per mol of silver. Then 4
0.3 g of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the average size was 0.06 μm.
Cubic silver iodobromide grains having a 87% plane ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, and then 0.1 g of phenoxyethanol was added thereto.
Ag 7.5.

(Preparation of Organic Acid Silver Emulsion A) Behenic acid
6 g and 300 ml of distilled water were mixed at 90 ° C for 15 minutes, 31.1 ml of a 1N-NaOH aqueous solution was added over 15 minutes with vigorous stirring, and the mixture was left as it was for 1 hour and then cooled to 30 ° C. Next, 7 ml of a 1N aqueous solution of phosphoric acid was added, and 0.13 g of (C-11) was added while stirring more vigorously. Then, the silver halide grains A prepared in advance were reduced to a silver halide amount of 1.25 mmol. It was added so that it might become. In addition, 1
25 ml of N-silver nitrate aqueous solution was continuously added over 2 minutes, and stirring was continued for 90 minutes. 37 g of a 1.2% by weight solution of polyvinyl acetate in butyl acetate was added to the aqueous mixture to form flocs of the dispersion, water was removed, washed twice with water and removed, and then polyvinyl butyral was added. 2.5% by weight of butyl acetate and isopropyl alcohol (denka butyral # 3000-K, manufactured by Denki Kagaku Kogyo KK)
After adding 20 g of the mixed solution 2 with stirring, 7.8 g of polyvinyl butyral (Denka butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK) was added to the thus obtained mixture of the organic acid and the silver halide. -57 g of butanone was added and dispersed with a homogenizer to obtain a silver behenate emulsion (acicular particles having an average minor axis of 0.06 µm, an average major axis of 1 µm, and a variation coefficient of 30%).

[0099]

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(Preparation of Emulsion Layer Coating Solution A) Each of the chemicals was added to the above-obtained organic acid silver emulsion in the following amount per mole of silver. At 25 ° C., sodium phenylthiosulfonate 25 mg, sodium phenylsulfinate 25 mg,
(C-1) 1.0 g, sensitizing dye A 0.65 g, (C-2) 2.1
g, 14.2 g of (C-3), 580 g of 2-butanone, 220 g of dimethylformamide and 32 g of methanol were added with stirring, and the mixture was allowed to stand for 3 hours. Then (C-4) 14.1
g, (C-5) 125 g, hydrazine derivative (C-6) 0.61
g, dyes of the present invention and comparative dyes (7
Amount at which transmission absorption at 80 nm becomes 0.5), Megafax
1.1 g of F-176P (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) and 3.7 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) were added with stirring.

[0101]

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CAB171-15S (Eastman Chemical Co., Ltd.)
45g, 2-butanone 1520
g, ethyl acetate 10 g, dimethylformamide 50 g,
(C-7) 1.4 g, (C-8) 11.6 g, (C-9) 5.4 g,
(C-10) 4.0 g, Megafax F-176P 0.43 g, Sildex H31 (Torkai Chemical Co., Ltd., spherical silica average size 3 μm) 1.2 g, sumidur N3500 (Sumitomo Bayer Urethane Co., Ltd.) A solution prepared by adding and dissolving a solution of 42 g in 4.2 g of ethyl acetate was prepared.

[0103]

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(Preparation of Support Having Back Surface) 6 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK), Sildex H121 (average size of spherical silica 12 μm manufactured by Dokai Chemical Co., Ltd.) 0 .2g, Sildex H51 (average size of spherical silica 5μm, manufactured by Dokai Chemical Co., Ltd.)
0.2 g and 0.1 g of Megafax F-176P2-propanol were added with stirring to 64 g and dissolved and mixed. Further, 10 g of methanol, 20 g of acetone, and 20 g of dimethylformamide 2 were added to the dye of the present invention and a comparative dye (an amount of the kind shown in Table 5 that the transmittance and absorption at 780 nm becomes 0.7).
A mixed solution of 0 g and a solution of 0.8 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) in 6 g of ethyl acetate were added to prepare a coating solution.
Apply the coating solution on the back side to a polyethylene terephthalate film with a moisture-proof undercoat containing vinylidene chloride on both sides.
Coating was performed so that the optical density at 80 nm was 0.7.

The coating solution for the emulsion layer was coated on the support prepared as described above so that the silver content was 1.6 g / m ^2, and the coating solution for the emulsion surface protective layer was dried on the emulsion surface to a dry thickness of 1.8 μm. It applied so that it might become.

(Evaluation of photographic performance)
Exposure under two conditions, each using a heat drum
Heat development was performed at 15 ° C. for 25 seconds. It was exposed to xenon flash light having an emission time of 10 ^-4 sec through an interference filter having a peak at 780 nm and a step wedge. It was exposed to xenon flash light having an emission time of 10 ^-4 sec through two conditions: an interference filter having a peak at 780 nm, a step wedge, and a tint net having a dot area ratio of 50%. The unexposed sample was heated at 115 ° C. for 25 using a heat drum.
The heat development was performed for 2 seconds. Density measurement of the resulting image,
The dot area ratio measurement and the spectral absorption measurement were performed, and the performance was evaluated by the following items.

ΔS (50-60); Absolute value of the difference between S50 and S60 S50; -log (reciprocal of the exposure required to obtain a dot area ratio of 60%) S60; -log (dot area ratio of 50% Therefore, the larger ΔS (50-60) is, the smaller the change in the halftone dot area ratio due to the exposure is, which is preferable. D360 nm, D410 nm; spectral absorption was measured after heat-treating the coated sample without exposure, and the absorbance at 360 nm and 410 nm was determined. It was expressed as the difference in concentration from the absorbance at each wavelength without the dye. This characteristic is a wavelength characteristic corresponding to the printing wavelength of the PS plate or the printer light source for returning, and the smaller the numerical value, the more easily the printing can be performed in a short time. Color: the same evaluation method as in Example 2 The results are shown in Table 5.

[0108]

[Table 5]

(Results) The samples of the present invention were obtained at 360 nm and 4 nm.
The absorption of 10 nm was small, and the variation of the halftone dot area ratio due to the exposure amount was small, and favorable photosensitive material characteristics were obtained.

Example 7 The same procedure as in Example 6 was carried out except that the hydrazine derivative (C-6) of Example 6 was replaced with the following, and the amount of addition was adjusted so that G0330 was within the range of Example 6, and added. When a sample was prepared and evaluated for photographic performance, the sample according to the present invention exhibited good performance as in Example 6.

[0111]

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──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FIG03C 8/52 C07D 239/70 // C07D 239/70 277/64 277/64 277/76 277/76 487/04 146 285 / 12 B41M 5/26 Y 487/04 146 C07D 285/12 A

Claims (2)

[Claims] 1. A naphthooxazinine squarylium compound represented by the following general formula (1). Embedded image Wherein, R ^1, R ^2, R ^3, R ^4, R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or aralkyl group, R ¹ and R
² and / or R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered ring. R ⁷ and R ⁸ represent a hydrogen atom or a monovalent group, and n represents an integer of 1 to 3. 2. A recording material comprising at least one dye represented by the general formula (1).