JPH0679146B2 - Thermal development color diffusion photosensitive material for CRT - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention (Field of Industrial Application) The present invention relates to an improved method and a photographic light-sensitive material for converting an electric signal into light and recording it as a color image on the photographic light-sensitive material.

(Prior Art) Various methods are known for converting an electric signal corresponding to a color image into light and obtaining a high-quality color hard copy by using a photographic light-sensitive material. For example, a method that directly takes an image on a CRT by instant color by a color diffusion transfer method, or various photographic films and photographic papers can be displayed in blue, green and red by an FSS (flying spot scanner) tube, which is a type of CRT. A method of scanning exposure through each filter, and three flat CRTs, which are a type of CRT, are used for each of the blue, green, and red signals (each corresponding fluorescent substance is painted so as to emit light for each color). There are known methods such as a split CRT method and a method using a flat CRT in which fluorescent substances of two or more colors are applied in strips. Also flat CRT
A similar method using OFT (optical fiber tube) which is one of the above is also known. There is also known a method of recording on a 16 mm film for movies by using three-color gas lasers (blue, green and red) (Journal of the Television Society 336 (I) 50-57 (1952)). A method using a light emitting diode or the like has also been proposed.

However, considering these writing methods, the method using a laser has drawbacks such as the need for an expensive and large-scale device because three lasers are used. Development is delayed and there are problems with arraying, so it is considered difficult to put it into practical use for the purpose of full-color use. Among these methods, the ones that are likely to become relatively small and inexpensive devices are considered to be the methods using CRT, and in particular, from the viewpoint of image quality, the scanning exposure method is used.

As the light-sensitive material used here, various materials such as 35 mm color negative, 35 mm color slide / conventional color paper, 16 mm motion picture film, Ektaflex, etc. are used, including the above-mentioned instant photographs.
Wet processing is disadvantageous due to the nature of a video printer that uses an electrical signal as a hard copy online. Among these, instato photography is preferable, but a major drawback is that the cost per hard copy is high.

Also, when using ordinary photosensitive materials for printing (for example, color paper, Ektaflex, etc.), these photosensitive materials have characteristics matching the color negative, so they are different from regular layers and ortho layers (here The spectrum and the photosensitivity maximum are relatively coincident.) The photosensitizing wavelength region of the panchromatic layer is on the considerably long-wave side of visible light (photosensitivity maximal wavelength is about 700 nm), and it is generally the same as that of the CRT red light-emitting phosphor. The light-sensitive maximum wavelengths of these light-sensitive materials do not match, and writing is performed only at the bottom of the spectral sensitivity distribution, resulting in extremely low efficiency.

(Object of the Invention) Accordingly, an object of the present invention is to provide an image with excellent writing performance, excellent developability and excellent image quality in a method of converting an electric signal into light and recording it as a color image on a photographic light-sensitive material. It is an object of the present invention to provide a method for easily and inexpensively obtaining and a color photographic light-sensitive material used therefor.

(2) Structure of the Invention An object of the present invention is to provide a photosensitive layer containing, on a support, at least one layer of a blue-sensitive silver halide, an organic silver salt, a dye-donor compound that forms a diffusible yellow dye, and a binder. At least one layer of green-sensitive silver halide, organic silver salt,
A light-sensitive layer containing a dye-donor compound that forms a diffusible magenta dye and a binder, and a light-sensitive layer containing at least one layer of a red-sensitive silver halide, an organic silver salt, a dye-donor compound that forms a diffusible cyan dye, and a binder. And the red-sensitive silver halide has a photosensitive maximum of 600 to 650 nm.
It is achieved by exposing a heat-developable color diffusion transfer light-sensitive material characterized by the following range by CRT and heat-development.

As the CRT, as described above, an FSS tube (flying spot scanner tube) as described in JP-A-58-31330, or JP-A-58-120240 and 58-120242.
CRT and OFT described in No. 58-121029, etc. are effectively used.

As a preferred embodiment of the present invention, on the support, in order from the side closer to the support, 600 to 50 nm, more preferably 610 to 640 nm.
A heat-developable red-sensitive layer having a light-sensitive maximum wavelength, a heat-developable green-sensitive layer having a light-sensitive maximum wavelength at 530 to 570 nm on the layer through a contact layer or an intermediate layer, and further directly or on the layer. Via a blue light cut dye layer), and a heat developable photosensitive material having a heat developable blue sensitive layer having a maximum photosensitive wavelength at 400 to 500 nm, wherein each layer is a dye of cyan, magenta and yellow. Thermal dye-based photosensitive materials containing compounds capable of forming or releasing are disclosed in, for example, JP-A-58-120240 and 58-
120240 and 58-121029, such as CRT (O
(Including FT) in which scanning exposure of blue, green and red light is performed in any order (in any order). In this embodiment, as described above, the sensitivity distributions of the regular layer and the ortho layer and the emission spectrum distributions of the CRT blue and green phosphors are also in good agreement with each other even in an ordinary light-sensitive material. The emission spectrum distribution of the body is 600 to 635 nm, which is considerably shorter than the maximum photosensitive wavelength of ordinary photographic light-sensitive materials, especially printing light-sensitive materials. By matching them, a great improvement in efficiency (shortening of writing time) can be achieved. These light-sensitive materials are exposed to light, for example, as described in JP-A-57-
179840, 57-186744, 57-198458, 57-20
7250, 58-123533, 58-149046, 58-1490
No. 47, Japanese Patent Application No. 57-229671, No. 58-33364, No. 58-109
As described in JP-A No. 293, etc., it is preferable that the dye is superposed on the image receiving layer, thermally developed, and the dye imagewise released or formed is transferred by thermal diffusion to the image receiving layer.

The light-sensitive material used in the present invention comprises a light-sensitive layer composed of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer each having a maximum light-sensitivity wavelength of 400 to 500 nm, 500 to 600 nm and 600 to 650 nm, respectively. A variety of photosensitizing dyes are used to impart properties, but the typical one is "The Theory of the Ph
otographic Process "3rd edition CEKenneth Mees, THJame
Any of those listed on pages 198 to 232 by S. can be used.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl,
Examples include hemicyanine and oxonol. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridineoxazole, thiazole, selenazole, and imidazole are more preferable. Such a nucleus may have an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a condensed carbocyclic or heterocyclic ring. Good. It may be symmetrical or asymmetrical, or methylene chain,
The polymethylene chain may have an alkyl group, a phenyl group, an enamine group, or a heterocyclic substituent.

The merocyanine dye may be, for example, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus in addition to the above basic nucleus,
It may have an acidic nucleus such as a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinthione nucleus, a malononitrile nucleus and a pyrazolone nucleus. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivative,
Azaindene cadmium salt, organic sulfonic acid and the like can be used in combination with a supersensitizing additive which does not absorb visible light as described in the specifications of US Pat. Nos. 2,933,390 and 2,937,089.

Examples of these dyes are, for example, Japanese Examined Patent Publication Nos. 43-4924 and 49-49.
18808, U.S. Pat.No. 3,761,279, JP-A-49-84637
No. 49-105524, No. 50-104637, No. 50-105127
No. 51-120715, No. 51-27924, No. 52-80829
Japanese Patent Publication No. 56-19618, U.S. Pat.No. 4,105,451, Japanese Patent Publication No. 57-46052, Japanese Patent Publication No. 56-164338, No. 57-19731,
No. 57-26843 and the like.

As the sensitizing dye used for the red-sensitive silver halide of the light-sensitive material of the present invention, those having a maximum wavelength of 600 to 650 nm, more preferably 610 to 640 nm, can be used. Among the trinuclear merocyanine dyes and cyanine dyes described in -18808, thiazoline, oxazoline, pyrroline, pyridine, quinoline, oxazole, thiazole, selenazole, carbocyanine dyes having a basic nucleus such as imidazole, dicarbocyanine dyes and Complex cyanine (trinuclear or tetranuclear) and the like are preferable.

The following are typical examples, but the present invention is not limited thereto.

The sensitizing dye used in the green-sensitive and blue-sensitive silver halide of the light-sensitive material of the present invention may be a sensitizing dye known in this field, and those used in the green-sensitive silver halide have a maximum photosensitive wavelength of 500 to 600 nm. Is suitable, and it is advantageous to use a blue-sensitive silver halide which does not use a sensitizing dye or which has a maximum photosensitive wavelength in the range of 400 to 500 nm. These dyes include polymethine dyes, cyanines, merocyanines, cyanine and merocyanine complexes, namely tri-, tetra- and polynuclear cyanines and merocyanines, oxonol, hemioxonol, styryl, merostyryl and streptocyanine, and two or more spectral sensitizing dyes. May be used in combination, or supersensitization can be performed by selectively combining with other additives. This is also described in detail in JP-A-58-111934.

Spectral sensitization can be carried out at any stage of emulsion preparation heretofore known to be useful. In the industry, the most common step is chemical sensitization followed by spectral sensitization. However, in particular the spectral sensitization can be carried out simultaneously with or at the same time as the chemical sensitization, completely before the chemical sensitization and even before the completion of silver halide grain silver precipitation. These are taught in US Pat. Nos. 3,638,960 and 4,225,666. Introducing a spectral sensitizing dye into an emulsion, according to the teachings of US Pat. No. 4,225,666, causes a portion of the spectral sensitizing dye to be present before chemical sensitization and the remaining portion to be introduced after chemical sensitization. A method is also possible.

The addition amount of the sensitizing dye is appropriately in the range of about 10 ⁻⁴ to 1 mol per mol of silver halide or silver halide-forming component.

The CRT phosphor used in the present invention has a blue color of 4
Those having an emission peak at 00 to 500 nm, 500 to 600 nm for green, and 600 to 650 nm for red are used.

Of these, the representative ones are P2 for blue.
2-B1 (Cub.ZnS: Ag), P5-B1 (CaWo ₄ ), P7-B1 (hex.
ZnS: Ag), P11-B1 (Cub.ZnS: Ag), P37 (ZnS: Ag, Ni) P
_{47 (Y 2 S; O 5} : Ce), LDP-B1 (Cub.ZnS: Ag + In 2 o 3), LDP
−B2 (Cub.ZuS: Ag ＋ In ₂ o ₃ ), P5 (CaWo ₃ : W), P7 (ZnS:
Ag + (ZnCd) S: Cu), P16 (CaMgS: O ₇ : Ce), P4-K (ZnS: Ag) for both blue and green (combines filters)
+ (Zn, CdS: Cu)), P4-A (ZnS: Ag + ZnS: Au, Al + Y ₂ O ₂
S: Eu), P4-M (ZnS: Ag + (Zn, Cd) S: Ag), P4-AA
((Zz, Cd) S: Au, Ag, Al), P17 (ZnO: Zn + (Zn, Cd) S: C
u), P40 (ZnS: Ag ＋ (Zn, Cd) S: Cu), P45 (Y ₂ O ₂ S: T
b), P15 (ZnO: Zn), P35 (Zn (S, Se): Ag) for green
P22-GN4 (Cub, ZnS: Cu, Al), P22-GK4 ((Zn, Cd) S: C
u, Al), P22GY (ZnS: Cu, Au, Al), LDP-G1 (ZnS: Cu, Al)
_{+ In 2 O 3), P1} -G1 (Zn 2 S: O 4: Mu), P2-G2 (hex, ZnS: C
u), P7-Y1 ((Zn, Cd) S: Cu), P24 (ZnS: Zn), P28
(Hex, ZnS: Ag, Cu), P31-G1 (Cub, ZnS: Cu), P34 (Zn
S: Pb, Cu), P36 ((Zn, Cd) S: Ag, Ni), P39 (Zn ₂ S: O ₄ : M
n, As), P42 (ZnS: Cu + Zn ₂ S: O ₄ : Mn, As), P43 (Cd ₂ O ₂ S:
Tb), P44 (Ld ₂ O ₂ S: Tb), P46-Y1 (Y ₃ Al ₅ O ₁₂ : Ce), P4
_{6-Y2 (Y 3 (Al} , Ga) 5 O 12: Ce), LA-GN (ZnS: Cu, Al),
LA-G3 ((Zn, Cd) S: Ag), SrGd ₂ S ₄ : Eu ²⁺ , P20 ((Zn, C
d) S: Ag), as it is for red _{P22-RE1 (Y 2 O 2} : Eu), P22-R
E2 (YVO ₄ : Eu), P22−RE3 (Y ₂ O ₂ S: Eu), P22−HCR2 (Y _{2
O 2 S: Eu + Pigment)} , LDP-R1 (Y 2 O 2 S: Eu + In 2 O 3), LDP
-R2 ((Zn, Cd) S : Ag + In 2 O 3), P13 (MgS: O 3: Mn), P2
5 (CaS: O ₃ : Pb, Mn), P27−R1 (Zn ₃ (PO ₄ ) ₂ : Mn), P27
-R2 ((Zn, Mg) ₃ (PO ₄ ) ₂ : Mn), etc., and P4-A (ZnS: Ag + ZnS: Au, Al), + Y ₂ O for other colors
₂ S: Eu, P14 (ZnS: Ag + (Zn, Cd) S: Cu), P49 (Zn ₂ S: O ₄ :
Mu ＋ YVO ₄ : Eu), P50 ((Zn, Cd) S: Cu, Ni ＋ Y ₂ O ₃ : Eu), P
51 ((Zn, Cd) S : Ag, Ni + YVO 4: Eu) phosphor of the like.

Among these emitters, the emission peak of the red emitter is 660 to 6
50 nm or most of them is 610 nm to 630 nm, and the maximum photosensitive wavelength of the panchromatic layer of ordinary print photosensitive materials such as color pepper and Ektaflex is around 700 nm, and the part of the sensitivity is used when writing to this. Nothing more than.

Therefore, according to the present invention, in the heat-developable color light-sensitive material, unlike the usual print light-sensitive material, the light-sensitive maximum of the red-sensitive layer is set to the light-emission maximum peak of the red-emitting phosphor of CRT (of which the most is between 600 and 650 nm). Yes, among them, the concentration is in the range of 620 to 630 nm.), And the efficiency of writing by the light emission of the CRT is significantly improved.

Further, the silver halide grains in the panchromatic layer can be made into fine particles, and the image quality can be improved. Further, especially in the case of heat-developable light-sensitive materials, fine graining of silver halide leads to further improvement in developability, which enables thinning of the panchromatic layer and further improves image quality. In the case of a light-sensitive material, the transferability of the dye released or formed can be improved, which is advantageous.

Therefore, by using the light-sensitive material of the present invention and writing by CRT, a high-quality hard copy print can be obtained by a low-priced and simple process.

Examples of dye-donor substances used in the present invention include those disclosed in JP-A-
57-179840, 58-58543, etc., JP-A-58-149046, JP-A-58-149047, JP-A-59-124339.
It is possible to use those described in Japanese Patent Application No. 58-33364 and Japanese Patent Application No. 58-109293.

Among the dye-donor substances used in the present invention, preferred ones are, for example, those described in detail in Japanese Patent Application Nos. 57-229671 and 58-33364, which have hydrophilicity such as sulfo group and carboxy group. It is also preferable to have a group or a group capable of immobilizing the dye-donor substance in the photothermographic layer such as a hydrophobic ballast group having a large molecular weight, and it is preferable that the dye formed or released by heat development has a thermal transfer property. .

The dye-providing substance particularly advantageously used in the present invention is a dye-forming compound represented by the following general formula (1).

General Formula (1) AB In the formula, A is a hydrophobic coupler residue, and this group immobilizes these dye-donor substances such as sulfo group, carboxyl group, and thiosulfo group in the photothermographic layer. Does not include groups.

B is a group that can be removed from the coupler by a coupling reaction, and has a large hydrophobic group such as a sulfo group, a carboxyl group, and a thiosulfo group (for example, an alkyl group having C ₈ or more, an alkyl group having C ₄ or more). It has an aryl group or a group that immobilizes a dye-donor substance such as a hydrophilic or hydrophobic polymer residue in the heat-developable photosensitive layer. A hydrophobic thermal transfer dye is produced by a coupling reaction with an oxidized product of a developing agent, and for example, A is preferably a group represented by the following general formulas (2) to (6).

General formula (2) General formula (3) General formula (4) General formula (5) General formula (6) In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms). , For example methyl, ethyl, butyl, t-octyl,
Examples thereof include groups such as n-dodecyl, n-pentadecyl, and cyclohexyl. Further, an aryl group such as a phenyl group may be substituted with a benzyl group or a phenethyl group), or a substituted or unsubstituted aryl group. A group (for example, a phenyl group, a naphthyl group, a tolyl group,
Methyl group), acyl group (eg acetyl group, tetradecanoyl group, piparoyl, substituted or unsubstituted benzoyl group), alkyloxycarbonyl group (eg methoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group (eg phenoxy) Carbonyl group, p-tolyloxycarbonyl group, α-naphthoxycarbonyl group, alkylsulfonyl group (eg methylsulfonyl group), arylsulfonyl group (eg phenylsulfonyl group), carbamoyl group (eg substituted or unsubstituted alkylcarbamoyl group) , A methylcarbamoyl group, a butylcarbamoyl group, a tetradecylcarbamoyl group, an N-methyl-N-dodecylcarbamoyl group, an optionally substituted phenoxyalkylcarbamoyl group, specifically 2,4-di-t-a- Roh phenoxy-butylcarbamoyl group, a substituted or unsubstituted phenylcarbamoyl group,
Specifically, a 2-dodecyloxyphenylcarbamoyl group or the like), a substituted or unsubstituted acylamino group (for example, n
-Butyramide, laurylamide, optionally substituted β
-Phenoxyethylamide group, phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamidoethylamide group, β-methoxyethylamide group), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, For example, methoxy group, ethoxy group, octadecyloxy group), sulfamoyl group (eg, methylsulfamoyl group, n-dodecylsulfamoyl group, substituted or unsubstituted phenylsulfamoyl group, specifically dodecylphenylsulfamoyl group) Group), a sulfonylamino group (for example, a methylsulfonylamino group, a tolylsulfonylamino group) or a hydroxyl group. Also
R ₁ and R ₂ may combine with each other to form a saturated or unsaturated 5- or 6-membered ring.

R ₅ , R ₆ and R ₇ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms such as methyl or ethyl group), Alkoxy group (preferably alkoxy group having 1 to 2 carbon atoms, for example, methoxy group, ethoxy group), substituted or unsubstituted alkylamido group (for example, laurylamido group), or optionally substituted phenoxyalkylamido group ( For example, an alkyl-substituted phenoxyacetamide group, etc.), a substituted or unsubstituted arylamide group, etc. are represented.

Further, R ₈ is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, for example, a methyl group, a butyl group, a heptadecyl group), an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, for example, a methoxy group, An ethoxy group, an octadecyloxy group), an arylamino group (for example, an anilino group, and an anilino group substituted with a substituent such as a halogen atom, an alkyl group, an amide group or an imide group), a substituted or unsubstituted alkylamide group ( For example, laurylamide, phenoxyacetamide which may be further substituted,
Phenoxybutanamide group) and a substituted or unsubstituted arylamide group (for example, a benzamide group, and a benzamide group further substituted with a halogen atom, an alkyl group, an alkoxyamide group, etc.).

R ₉ represents an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms) or a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, methoxyphenyl group, etc.).

Further, R ₁₀ is an arylamino group (for example, an anilino group,
Further, it represents an anilino group substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, an imide group or the like.

R ¹ which is a substituent of the coupler residue represented by A
R ¹⁰ preferably has an aryl group having a C ₈ or more alkyl group and / or a C ₄ or more alkyl group so as not to impair the thermal transfer property of the formed dye.

In the general formula (1), B is a hydrophilic group such as a sulfo group or a carboxy group or a group represented by -J-Y (where J is
Represents a divalent linking group, and Y represents a substituted or unsubstituted alkyl group or aryl group. ) More specifically, as the divalent linking group represented by J, —O, —S—, —NHCO—, —NHSO—, —O—SO ₂ — and the like can be mentioned, and the alkyl group or aryl group represented by Y is an alkyl substituted with a hydrophilic group such as a sulfo group or a carboxyl group. Groups or aryl groups are preferred. Among them, an alkylcarbamoyl group which may be further substituted, an alkyl group substituted with an arylcarbamoyl group, a carboalkoxy group, an alkyl substituted with a carboaryloxy group, an alkyl group substituted with a halogen atom, or a substituted An aryl group substituted with an alkylamide group, an alkylsulfonamide group, an arylamide group, an arylsulfonamide group, etc., an optionally substituted alkylcarbamoyl group, an alkylsulfamoyl group, an arylcarbamoyl group, an arylsulfamoyl group Group, an aryl group substituted by a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, an aryl group substituted by an optionally substituted alkyl group having 1 to 22 carbon atoms, and 1 carbon atom An aryl group substituted with an alkylamino group of ~ 22 Other, halogen atom, a hydroxyl group,
An aryl group substituted with a sulfo group, a carboxy group, a sulfamoyl group or the like is particularly preferable.

The active site substituent represented by B as described above is a hydrophilic group such as a sulfo group or a carboxyl group for immobilizing the whole coupler molecule against heat in the layer containing the entire coupler molecule.
It is preferable to have a group capable of immobilizing the dye-donating substance such as an aryl group having a C ₈ or more alkyl group or a C ₄ or more alkyl group, and more preferable is a hydrophilic group and C _It is more preferable that they both have ₈ or more alkyl groups or aryl groups having C ₄ or more alkyl groups.

Of the above-mentioned hydrophilic groups, particularly preferable ones are:
Sulfo group, sulfino group, sulfeno group, thiosulfo group, dithiosulfo group, hydroxysulfonyloxy group,
A hydroxysulfonylthio group, a carboxy group, a thiocarxyl group and the like, which are described in detail in the above-mentioned Japanese Patent Application No. 58-33364.

Further, as a dye-donor compound, JP-A-58-149047, Japanese Patent Application No.
It is also preferable to use the polymer couplers described in 58-109293 and the like.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples thereof include silver chloroiodobromide or a mixture thereof. The silver halide may be coarse grains or fine grains, but the preferable grain size is about 1.5 μm to about 0.0 μm.
01 μm, more preferably about 0.5 μm to about 0.01 μm
m.

The photosensitive silver halide can be prepared by any method known in the photographic art, such as a single jet method and a double jet method.

The photosensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Examples of the sensitizing method include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt forming component may be allowed to coexist with an organic silver salt to form photosensitive silver halide on a part of the organic silver salt. The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MX _n (wherein M represents an H atom, an NH ₄ group or a metal atom, and X represents Cl, Br. Alternatively, I and n are 1 when M is a H atom and NH ₄ group, and their valences are when M is a metal atom, which may be lithium, sodium, potassium, rubidium, cesium, copper or gold. , Beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt , Nickel, rhodium, palladium, osmium, iridium, platinum,
Examples include cerium. ), A halogen-containing metal complex (for example, K ₂ PtCl ₆ ,, K ₂ PtBr ₆ ,, HAuCl ₄ ,, (NH ₄ ) ₂ IrCl ₆ ,, (NH ₄ ) ₃ I
Cl ₆ , (NH ₄ ) ₂ RuCl ₆ , (NH ₄ ) ₃ RuCl ₆ , (NH ₄ ) ₃ RhCl ₆ , (NH
₄ ) ₃ RhBr ₆ etc.), onium halides (eg, tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, quaternary ammonium halides such as trimethylbenzylammonium bromide, tetraethylphosphorus). Quaternary phosphonium halides such as bromide, benzylethylmethyl bromide, tertiary sulfonium halides such as 1-ethylthiazolium bromide), halogenated hydrocarbons (eg iodoform, bromoform carbon tetrabromide, 2- Brom-2-methylpropane, etc.), N-
Halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-
Bromacetamide, N-iodosuccinimide, N-
Bromphthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.) ,
Other halogen-containing compounds (eg triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-
Brom ethanol etc.) and the like.

These photosensitive silver halide and photosensitive silver salt-forming component can be used in combination in various methods, and the amount used is 0.001 mol to 5.0 mol, preferably 0.01 mol to 2.0 mol, per 1 mol of organic silver salt. Is.

Examples of the organic silver salt used in the heat-developable color light-sensitive material of the present invention include JP-B Nos. 43-4924, 44-26582, and 45-184.
16, 45-12700, 45-22185 and JP-A-49-
52626, 52-31728, 5213731, 52-141222
No. 53-362224, No. 53-37610 publications, U.S. Pat.Nos. 3,330,633, 4,168,980 and the like, silver salts of aliphatic carboxylic acids described in the specification, for example, silver laurate,
Silver myristate, silver palmitate, silver stearate, silver arachidonic acid, silver behenate, etc., and aromatic silver carboxylates, such as silver benzoate, silver phthalate, etc., and silver salts having an imino group, for example, benzotriazole silver. , Silver saccharin, silver phthalazinone, silver phthalimide and the like, silver salts of compounds having a mercapto group or a thione group, for example, 2-mercaptobenzo-oxazole silver, mercaptooxadiazole silver, mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3 -Mercapto-phenyl-1,2,4-triazole silver, and also 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene silver,
Examples thereof include 5-methyl-7-hydroxy-1,2,3,4,6, -pentazaindene silver.

RD16966, 16907, British Patent No. 1,590,956,
A silver compound as described in the specification of 1,590,957 can also be used. Among them, for example, a silver salt having an imino group such as a silver salt of benzotriazole silver is preferable, and examples of the silver salt of benzotriazole include alkyl-substituted benzotriazole silver such as methylbenzotriazole silver, for example, bromo-benzotriazole silver and chloro. Halogen-substituted benzotriazole silver such as benzotriazole silver, amide-substituted benzotriazole silver such as 5-acetamidobenzotriazole silver, and British Patent 1,590,
Compounds described in each specification of No. 956 and No. 1,590,957, for example, N- [6-chloro-4-N (3,5-dichloro-4-hydroxyphenyl) imino-1-oxo-5-methyl-
2,5-Cyclohexadien-2-yl] -5-carbamoylbenzotriazole silver salt, 2-benzotriazol-5-ylazo-4-methoxy-1-naphthol silver salt,
1-benzotriazol-5-ylazo-2-naphthol silver salt, N-benzotriazol-5-yl-4- (4
-Dimethylaminophenylazo) benzoamide silver salt and the like.

Further, nitrobenzotriazoles represented by the following general formula (7) and benzotriazoles represented by the following general formula (8) can be advantageously used.

General formula (7) In the formula, R ₁₁ represents a nitro group, R ₁₂ and R ₁₃ may be the same or different and each is a halogen atom (for example, chlorine, bromine, iodine), a hydroxy group, a sulfo group or a salt thereof (for example, a sodium salt, Potassium salt, ammonium salt), carboxy group or salt thereof (eg sodium salt, potassium salt, ammonium salt), nitro group, cyano group, or optionally substituted carbamoyl group, sulfamoyl group, alkyl group (eg methyl group) Base,
It represents an ethyl group, a propyl group, an alkoxy group (for example, a methoxy group, an ethoxy group), an aryl group (for example, phenyl) or an amino group, m is 0 to 2, and n is 0 or 1.
Represents Further, as the substituent of the carbamoyl group,
For example, a methyl group, an ethyl group, an acetyl group and the like can be mentioned, and examples of the substituent of the sulfamoyl group can include a methyl group, an ethyl group and an acetyl group,
Examples of the substituent of the alkyl group include a carboxy group and an ethoxycarbonyl group, examples of the substituent of the aryl group include a sulfo group and a nitro group, and examples of the substituent of the alkoxy group include a carboxy group and an ethoxycarbonyl group. And the substituent of the amino group can include, for example, an acetyl group, a methanesulfonyl group, and a hydroxy group.

The compound represented by the general formula (7) is a silver salt of a benzotriazole derivative having at least one nitro group, and specific examples thereof include the following compounds.

For example, 4-nitrobenzotriazole silver, 5-nitrobenzotriazole silver, 5-nitro-6-chlorobenzotriazole silver, 5-nitro-6-methylbenzotriazole silver, 5-nitro-6-methoxybenzotriazole silver, 5- Nitro-7-phenylbenzotriazole silver,
4-hydroxy-5-nitrobenzotriazole silver, 4
-Hydroxy-7-nitrobenzotriazole silver, 4-
Hydroxy-5,7-dinitrobenzotriazole silver, 4
-Hydroxy-5-nitro-6-chlorobenzotriazole silver, 4-hydroxy-5-nitro-6-methylbenzotriazole silver, 4-sulfo-6-nitrobenzotriazole silver, 4-carboxy-6-nitrobenzotriazole silver , 5-carboxy-6-nitrobenzotriazole silver, 4-carbamoyl-6-nitrobenzotriazole silver, 4-sulfamoyl-6-nitrobenzotriazole silver, 5-carboxymethyl-6-nitrobenzotriazole silver, 5-hydroxycarbonyl Methoxy-6
-Nitrobenzotriazole silver, 5-nitro-7-cyanobenzotriazole silver, 5-amino-6-nitrobenzotriazole silver, 5-nitro-7- (p-nitrophenyl) benzotriazole silver, 5,7-dinitro- Examples thereof include 6-methylbenzotriazole silver, 5,7-dinitro-6-chlorobenzotriazole silver, and 5,7-dinitro-6-methoxybenzotriazole silver.

General formula (8) In the formula, R ₁₄ has a hydroxy group, a sulfo group or a salt thereof (eg sodium salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (eg sodium salt, potassium salt, ammonium salt), or a substituent. Represents a carbamoyl group which may be substituted or a sulfamoyl group which may have a substituent, and R ₁₅ is a halogen atom (eg chlorine, bromine, iodine), a hydroxy group, a sulfo group or a salt thereof (eg sodium salt, potassium salt, ammonium salt). ), A carboxy group or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, nitro group, cyano group, or an alkyl group which may have a substituent (for example, methyl group, ethyl group, propyl group), aryl group) , (Eg phenyl group), alkoxy group (eg methoxy group, ethoxy group) or It represents an amino group, p 1 or 2, q is an integer of 0 to 2.

Further, examples of the substituent of the carbamoyl group for R ₁₄ include a methyl group, ethyl group and acetyl group, and examples of the substituent of the sulfamoyl group include a methyl group, ethyl group and acetyl group. be able to. Further, examples of the substituent of the alkyl group in R ₁₅ include a carboxy group and an ethoxycarbonyl group, examples of the substituent of the aryl group include a sulfo group and nitro group, and examples of the substituent of the alkoxy group include carboxy. Examples of the substituent of the group, the ethoxycarbonyl group, and the amino group include an acetyl group, a methanesulfonyl group, a hydroxy group, and the like.

Specific examples of the organic silver salt represented by the general formula (8) include the following compounds.

For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sulfonate, benzotriazole silver-5-sulfonate, benzo Silver triazol-4-sulfonate, potassium benzotriazole-5-sulfonate, ammonium benzotriazole-4-sulfonate, ammonium benzotriazole-5-sulfonate, silver 4-carboxybenzotriazole, 5-carboxybenzo Triazole silver, sodium benzotriazole-4-carboxylate, sodium benzotriazole-5-carboxylate, potassium benzotriazole-4-carboxylate,
Benzotriazole silver-5-carboxylate potassium, benzotriazole silver-4-carboxylate ammonium, benzotriazole silver-5-carboxylate ammonium, 5-
Carbamoylbenzotriazole silver, 4-sulfamoylbenzotriazole silver, 5-carboxy-6-hydroxybenzotriazole silver, 5-carboxy-7-sulfobenzotriazole silver, 4-hydroxy-5-sulfobenzotriazole silver, 4-hydroxy -7-sulfobenzotriazole silver, 5,6-dicarboxybenzotriazole silver, 4,6-dihydroxybenzotriazole silver,
4-hydroxy-5-chlorobenzotriazole silver, 4
-Hydroxy-5-methylbenzotriazole silver, 4-
Hydroxy-5-methoxybenzotriazole silver, 4-
Hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-5-cyanobenzotriazole silver, 4-hydroxy-5-aminobenzotriazole silver, 4-hydroxy-5-acetamidobenzotriazole silver, 4-hydroxy-5-benzenesulfone Amidobenzotriazole silver, 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-
Hydroxy-5-carboxymethylbenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethylbenzotriazole silver, 4-hydroxy-5-phenylbenzotriazole silver, 4-hydroxy-5- (p-nitrophenyl) benzotriazole silver, 4-hydroxy-
5- (p-sulfophenyl) benzotriazole silver, 4
-Sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5
-Methoxybenzotriazole silver, 4-sulfo-5-cyanobenzotriazole silver, 4-sulfo-5-aminobenzotriazole silver, 4-sulfo-5-acetaminobenzotriazole silver, 4-sulfo-5-benzenesulfonamidebenzo Triazole silver, 4-sulfo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-
Sulfo-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxybenzotriazole silver, 4-sulfo-5-carboxymethylbenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethylbenzotriazole silver, 4-sulfo -5-Phenylbenzotriazole silver, 4-sulfo-5- (p-nitrophenyl) benzotriazole silver, 4-sulfo-5-
(P-Sulfophenyl) benzotriazole silver, 4-sulfo-5-methoxy-6-chlorobenzotriazole silver, 4-sulfo-5-chloro-6-carboxybenzotriazole silver, 4-carboxy-5-chlorobenzotriazole silver , 4-carboxy-5-methylbenzotriazole silver, 4-carboxy-5-nitrobenzotriazole silver, 4-carboxy-5-aminobenzotriazole silver, 4-carboxy-5-methoxybenzotriazole silver, 4-carboxy-5 -Acetamidobenzotriazole silver, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-5-carboxymethylbenzotriazole silver, 4-carboxy-5-phenylbenzotriazole silver, 4-carboxy-5- (p -Nitro Eniru) benzotriazole silver,
4-carboxy-5-methyl-7-sulfobenzotriazole silver etc. can be mentioned. These compounds may be used alone or in combination of two or more.

The organic silver salt used in the present invention can be prepared by a known method,
The isolated organic silver salt may be used by dispersing it in a binder by a suitable means, or may be prepared as a silver salt in a suitable binder and used as it is without isolation. Good.

The amount of the organic silver salt used is 0.05 g to 10.0 g, and preferably 0.2 g to 2.0 g per 1 m ² of the support.

Various binders can be used in the light-sensitive material of the present invention, but as a suitable binder, a hydrophilic binder can be arbitrarily used according to the purpose. For example, proteins such as gelatin and gelatin derivatives, cellulose derivatives,
It includes natural substances such as polysaccharides such as dextran, gum arabic, etc., vinyl compounds in the form of latex to increase the dimensional stability of photographic materials, and synthetic polymers as described below. Suitable synthetic polymers include U.S. Pat.Nos. 3,142,586, 3,193,386, 3,062,674,
Examples thereof include those described in the respective specifications of No. 3,220,844, No. 3,287,289, and No. 3,411,911. Effective polymers include alkyl acrylates, methacrylates, acrylic acids, sulfoalkyl acrylates or methacrylates to water insoluble polymers and the like.
Suitable polymeric substances include polyvinyl butyral, polyacrylamide cellulose acetate butyrate, cellulose acetate propionate, polymethylmethacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl chloride. -Vinyl acetate copolymer vinyl acetate-vinyl chloride-copolymer with maleic acid,
Polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose flopionate,
Cellulose acetate phthalate can be mentioned. Among these polymers, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, and cellulose acetate butyrate are particularly preferable. If necessary, two or more kinds may be mixed and used.

In the present invention, the binder is preferably a hydrophilic binder. The term "hydrophilic" as used herein means one that is soluble in water or a mixed solution of water and an organic solvent (a solvent that can be optionally mixed with water), and examples of hydrophilic binders include gelatin, Gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, natural substances such as gum arabic, and polyvinyl acetal as an effective polymer (preferably having an acetalization degree of 20% or less, for example, polyvinyl butyral), polyacrylamide, polyvinyl pyrrolidone, ethyl cellulose, Examples thereof include polyvinyl alcohol, (preferably having a saponification degree of 75% or more) and the like. These may be used as a mixture of two or more, if necessary.

The amount of the binder is preferably 1 to 10 to 10 parts by weight, more preferably 1 to 4 to 4 parts by weight relative to 1 part of the organic silver salt per each photosensitive layer, and 0.6 to 5 g per 1 m ^{2 of} the support (each layer). (In the total amount of the binders) is preferred.

The light-sensitive material of the present invention is disclosed in, for example, JP-A-57-179840 and 58-58.
In the case of -58543, a developing agent is not used or a black and white developing agent is generally used.
149047, 59-124339, Japanese Patent Application No. 58-33364, 58
In the case of -109293 or the like, a color developing agent is used.

As described above, the developing agent to be used varies depending on the color forming method, but preferred are JP-A Nos. 58-149046 and 58-149047.
No. 59-124339, Japanese Patent Application No. 58-33364, No. 58-10929.
This is the method disclosed in No. 3.

Preferred reducing agents used in the light-sensitive material of the present invention include, for example, U.S. Patent Nos. 3,531,286 and 3,761,270,
No. 3,764,328, each specification, Research Disclosure (hereinafter referred to as RRD) 1214
6, RD15108, RD15127 and JP-A-56-27132, p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoroamidophenol-based and sulfonamidephenol-based developing agents, and hydrazone-type color developing agents. Known color-developing agents such as main agents or their precursors are mentioned, and particularly preferred is JP-A
56-146133 and Japanese Patent Application No. 57-2259 filed by the present applicant.
No. 28, p- (N, N-dialkylaminophenyl) sulfamic acid developing agents.

These reducing agents may be used alone or in combination of two or more. The amount of the reducing agent used depends on the type of organic silver salt used, the type of photosensitive silver salt and the type of other additives, but is usually 0.05 mol to 10 mol per mol of the organic silver salt. %, And preferably 0.1 mol to 3 mol.

Various additives can be added to the heat-developable color light-sensitive material of the present invention, if necessary, in addition to the above components. For example, as a development accelerator, U.S. Patent Nos. 3,220,840 and 3,5
31,285, 4,012,260, 4,060,420, 4,
No. 088,496, No. 4,207,392 each specification or RD15733,
The 15734, the alkaline release agents described in such 15776, organic acids described in JP-B-45-12700, -CO described in U.S. Pat. No. _{3,667,959 -, - SO 2 -,} - SO- non-aqueous polar having the group Solvent compounds, melt formers described in U.S. Pat. No. 3,438,776, polyalkylene glycols described in U.S. Pat. No. 3,666,477, and JP-A-51-19525.

As the color toning agent, for example, JP-A-46-4928 and 46-6077.
No. 49-5019, 49-5020, 49-91215, 4
9-107727, 50-2524, 50-67132, 50-67
641, 50-114217, 52-33722, 52-99813
No. 53-1020, No. 53-55115, No. 53-76020, No.
53-125014, 54-156523, 54-156524, 54
-156525, 54-156526, 55-4060, 55-40
61, 55-32015, etc. and West German Patent No. 2,14
No. 0,406, No. 2,147,063, No. 22,220,618, U.S. Patent Nos. 3,080,254, No. 3,847,612, No. 3,782,941.
No. 3, No. 3,994,732, No. 4,123,82, No. 4,201,582
Phthalazinone, phthalisid, pyrazolone, quinazolinone, N-
Hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3-dihydro-1,3-oxazine-2,4-dione,
Oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyril, sulfonamide, 2H-1,3-benzothiazine-2,4- (3H) dione,
There are benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and a mixture of one or more of these with an imidazole compound, or an acid anhydride such as phthalic acid, naphthalic acid, etc. A mixture of at least one of the above and a phthalazine compound, and further a combination of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid and the like. Japanese Patent Application No. 57-73215 filed by the present applicant
No. 57-76838, 3-amino-
5-Mercapto-1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles are also effective.

Further, as an antifoggant, for example, Japanese Patent Publication No. 47-11
113, JP-A-49-90118, 49-10724, 49-9
7613, 50-101019, 49-130720, 50-1233
No. 31, No. 51-47419, No. 51-57435, No. 51-78227
No. 51-104338, No. 53-19825, No. 53-20923,
51-50725, 51-3223, 51-42529, 51-
81124, 54-51821, 55-93149, etc., as well as British Patent No. 1,455,271 and U.S. Patent No. 3,885,968.
No. 3,700,457, 4,137,079, 4,138,26
No. 5, West German Patent No. 2,617,907 and the like, which are compounds described in the respective specifications, such as mercuric salts, or oxidants (for example, N
-Halogenoacetamide, N-halogenosuccinimide, perchloric acid and salts thereof, inorganic peroxides, persulfates, etc., or acid and salts thereof (for example, sulfinic acid, lithium laurate, rosin, diterbenic acid, thiosulfonic acid) Etc.), or sulfur-containing compounds (for example, mercapto compound-releasing compounds, thiouracil, disulfide, sulfur alone, mercapto-1,2,4-triazole, thiazoline thione, polysulfide compounds, etc.), other, oxazoline, 1,2,4- Examples thereof include compounds such as triazole and phthalimide.

Further, as antifoggants, Japanese Patent Application Nos. 59-66380 and 5
Hydrophilic benzotriazole derivatives described in 9-56506 and the like, such as 4-sulfobenzotriazole, 5
A compound having a failing hydroxyl group such as carboxybenzotriazole or a hydroquinone derivative is effective, and the effect of preventing fog is further enhanced by using a hydrophilic benzotriazole derivative and a hydroquinone derivative together.

In addition, as a stabilizer, a print-out preventing agent after treatment may be used at the same time. For example, JP-A-48-45228 and JP-A-50-22828 may be used.
No. 119624, No. 50-120328, No. 53-46020, etc., halogenated hydrocarbons, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo. Examples include 2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole and 2,4-bis (tribromomethyl) -6-methyltriazine.

Also, Japanese Patent Publication No. 46-5393, Japanese Patent Laid-Open Nos. 50-54329, 50-770.
Post-treatment may be performed using an ionic compound as described in JP-A No. 34-34.

Furthermore, U.S. Pat.Nos. 3,301,678 and 3,506,444,
No. 3,824,1033, No. 3,844,788 isothiuronium-based stabilizer precursor described in each specification, also U.S. Patent No. 3,669,670, No. 4,012,260, No. 4,060,
It may contain an activator stabilizer precursor described in the specification of No. 420 or the like.

In addition to the above components, the heat-developable color light-sensitive material of the present invention may further contain, if necessary, a spectral sensitizing dye, an antihalation dye, a fluorescent whitening agent, a hardener, an antistatic agent, a plasticizer, a spreading agent, etc. Various additives and coating aids can be added.

The photosensitive layer containing the photosensitive silver halide, the organic silver salt, the dye-donor, the reducing agent and the binder, which are the constituents of the present invention, may be formed in one layer or in two layers in contact with each other. It may be configured separately.

In the heat-developable color light-sensitive material of the present invention, in addition to the above layers, it is preferable to provide an intermediate layer between the respective light-sensitive layers for the purpose of preventing color turbidity.

The intermediate layer may be a layer consisting of only a binder, but it may also contain a thermal solvent, an organic silver salt or a reducing agent contained in the photosensitive layer, and a compound (DP ') that scavenges an oxidant of the reducing agent. It is preferable to include a scavenger).

Particularly preferred compounds as the DP 'scavenger are:
It is a coupler having an immobile group as a substituent other than the active site.
Preferred examples of the immobile group include groups having a total number of carbon atoms of 8 or more and / or hydrophilic groups such as sulfo group and carboxy group, and polymer residues.

A concrete example of the above-mentioned DP 'scavenger is, for example, Japanese Patent Application No.
-237965.

As the binder used in the intermediate layer, a hydrophilic or hydrophobic binder is used, and a binder used in the photosensitive layer is particularly preferable.

The light-sensitive material of the present invention may have a protective film made of various polymers. As a preferable protective film, Japanese Patent Publication No. 54-11
No. 696, and the various lipophilic and hydrophilic synthetic and natural polymers described above which are used as the binder of the light-sensitive material of the present invention, and hydrophilic ones are particularly preferable. . Of these, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal and the like are preferable, and two or more kinds of these polymers may be used in combination.

Further, when these protective films or no protective film is contained, it is preferable to contain a matting agent in the uppermost layer of the light-sensitive material of the present invention.
In order to thermally transfer the heat transferable dye to the image receiving layer, adhesion between the image receiving layer and the photosensitive layer is an important factor. For this purpose, the uppermost layer of the photosensitive material, α contains a matting agent on the surface of the image receiving paper. Is preferred. Examples of matting agents used here include RD
Starch as listed in 9232, T: O ₂ , ZnO ₂ , silica and the like, and U.S. Pat.Nos. 2,992,101 and 2,701,245 described methacrylic acid-methyl methacrylate copolymer,
Examples thereof include polymethyl methacrylate, methyl methacrylate-styrene copolymer, polystyrene and the like.

The photosensitive layer and other layers containing the above components of the present invention are coated on a wide variety of supports. Examples of the support used in the present invention include cellulose nitrate films, cellulose ester films, polyvinyl acetal films, polyethylene films, polyethylene terephthalate films, plastic films such as polycarbonate films, and glass, paper, metals such as aluminum, and the like. . Also, baryta paper, resin coated paper, and water resistant paper can be used.

In addition to the above, a photographic constituent layer such as an undercoat layer, a packing layer or a filter layer may be provided.

The heat-developable color light-sensitive material of the present invention is imagewise exposed and then heat-developed to form an imagewise distribution of a heat transferable dye from the above dye-donor substance, and at least a part of the imagewise distribution is used as a light-sensitive material. A color image is formed by transferring to an image receiving member having a stacking relationship.

The transfer of the dye to the above-mentioned image receiving member is performed by, for example, methanol,
Acetonitrile, various transfer methods such as transfer using an organic solvent such as dimethylformamide or water, or heat transfer using a heat solvent, heat transfer transfer by sublimation of the dye itself, etc. can be used. When a thermal solvent is contained, the dye can be transferred only by bringing it into close contact with the image receiving member and heating.

The image receiving member may have a function of receiving the dye released or formed by heat development, and has a mordant used in a dye diffusion transfer type photosensitive material and a glass transition temperature described in JP-A-57-207250. It is preferably formed of a heat resistant organic polymer substance having a temperature of 40 ° C. or higher and 250 ° C. or lower.

Specific examples of the mordant, nitrogen-containing secondary, tertiary amines, nitrogen-containing heterocyclic compounds, these quaternary cationic compounds, U.S. Patent Nos. 2,548,564, 2,484,430, 3,4,
Vinyl pyridine polymers and vinyl pyridinium cation polymers disclosed in 148,061 and 3,756,814, polymers containing dialkylamino groups disclosed in U.S. Pat.No. 2,675,316, aminoguanidine derivatives disclosed in U.S. Pat. , U.S. Patent No. 3,
625,694, 3,859,096, British Patent No. 1,277,453,
A mordant capable of crosslinking with gelatin and the like disclosed in U.S. Pat. No. 2,011,012, U.S. Patent Nos. 3,958,995 and 2,721,852,
Aqueous sol mordants disclosed in JP-A-2,798,063, water-insoluble mordants disclosed in JP-A-50-61228, U.S. Pat.No. 3,788,855, West German patent application (OLS) No. 2,843,32
No. 0, JP-A-53-30328, JP-A-52-155528, JP-A-53-125
No. 53, No. 53-1024, No. 54-74430, No. 54-124726,
No. 55-22766, U.S. Pat.Nos. 3,642,482, and 3,488,706.
No. 3, No. 3,557,066, No. 3,271,147, No. 3,271,148,
Japanese Examined Japanese Patent Publication No. 55-29418, No. 56-36414, No. 57-12139, R
Various mordants disclosed in D12045 (1974) can be mentioned.

Particularly useful mordants are polymers containing ammonium salts,
It is described in US Pat. No. 3,709,690. For example, the polymer containing ammonium salt is polystyrene-co-N, N, N-tri-n-hexyl-N-vinylbenzylammonium chloride, and the ratio of styrene to vinylbenzylammonium chloride is 1: 4 to 4: 1. ,Preferably
It is 1: 1.

A typical image receiving layer for dye diffusion transfer is obtained by mixing a polymer containing an ammonium salt with gelatin and coating the mixture on a support. A transfer solvent can be used for transferring the dye from the photothermographic layer to the image receiving layer. As the transfer solvent, low boiling point solvents such as methanol, ethyl acetate and diisobutyl ketone and high boiling point solvents such as tri-n-cresyl phosphate and di-n-butyl phthalate are used.
In the case of a high boiling point solvent, it can be emulsified in gelatin using a suitable emulsifier and added to the image receiving layer.

Examples of the heat-resistant organic polymer substance include a molecular weight of 2000 to
85000 polystyrene, polystyrene derivatives having C4 or less substituents, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinylalcohol, polyvinylformal, polyvinylbutyral and other polyacetals, polyvinyl chloride , Chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly-N, N-dimethylallylamide, p-cyanophenyl group, pentachlorophenyl group and 2,4-
Polyacrylate with dichlorophenyl group, polyacrylchloroacrylate, polymethylmethacrylate,
Polyethylmethacrylate, polypropylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate, poly-tert-butylmethacrylate,
Examples thereof include polyesters such as polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate and polyethylene terephthalate, polysulfones, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides and cellulose acetates. Also, Polymer Handbook 2nd cd. (J. Brandr
Up, EHImmergut ed) John Wiley & Sons Publishing, synthetic polymers with a glass transition temperature of 40 ° C. or higher are also useful. These polymer substances may be used alone or in combination of two or more and used as a copolymer.

Particularly useful polymers include cellulose acetates such as triacetate and diacetate, terephthalic acid with heptamethylenediamine, fluorenedipropylpropylamine and adipic acid, hexamethylenediamine and diphenic acid,
Polyamide by a combination of hexamethylenediamine and isophthalic acid, polyester by a combination of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate, polycarbonate,
Examples include polyvinyl chloride. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene-
Polyethylene terephthalate using glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective.

The above-mentioned polymer is dissolved in a suitable solvent and applied on a support to form an image-receiving layer, or a film-like image-receiving layer comprising the above-mentioned polymer is laminated on the support and used, or applied on the support. Alternatively, the image-receiving layer can be composed of a member (for example, a film) made of the above-mentioned polymer alone (combined image-receiving layer / support type).

Further, the image receiving layer may be formed by providing an opaque layer (reflective layer) containing titanium dioxide dispersed in gelatin on the image receiving layer on a transparent support. With this opaque layer, a reflective color image can be obtained by viewing the transferred color image from the transparent support side of the image receiving layer.

Hereinafter, the present invention will be described more specifically with reference to Examples.
Embodiments of the present invention are not limited thereby.

Example 1 Red-sensitive silver halide emulsion (3,3'-di- (γ-sulfopropyl) -9 was added to a chemically aged silver iodobromide emulsion having a silver iodide content of 4 mol% and a grain size of 0.1 μm. -Methyl thiadicarbocyanine sodium salt (600 mg added per 1 mol of silver) is converted into silver to give 0.2 g of 4-sulfobenzotriazole and silver nitrate in an equimolar reaction in an aqueous poly (4-vinylpyrrolidone) solution. Converted to pH 6.0 and converted to silver 0.2g, 3-methyl-pentane-1,3,5-triol 1.6g, 4-diethylamino-2-methylphenylsulfamate sodium 0.4g, dye donating compound 2-acetamido-4- (1-carboxy-tridecyloxy) as
-5-methyl-6-chlorophenol 0.52g and 3-
Amino-4-allyl-5-mercapto-1,2,4-triazole 6mg, other gelatin, surfactant and gelatin hardener were added to the coating solution and photographic undercoating was applied. It was coated on a polyethylene terephthalate film. Silver, each coating amount of gelatin and poly ^{(4-vinylpyrrolidone) 1.2g / m 2, 1.25g /} m 2
And 2.9 g / m ² .

Next, an intermediate layer consisting of polyvinylpyrrolidone and gelatin was provided (gelatin 0.4 g / m ² , polyvinylpyrrolidone
1.0 g / m ² , but 3-methylpentane-1,3,5-triol
0.7 g / m ² and 1- (3,5-dicarboxyphenyl) -3
-(2-sulfohexadecanamide) pyrazolin-5-
Contains 0.3 g / m ^{2 of} on. ). Further on this, the red-sensitive silver halide emulsion was added to a green-sensitive silver halide emulsion (silver iodide content 4 mol%, average grain size 0.125 μm, cubic grains of chemically ripened silver iodobromide emulsion 3,3 ′ -Carboxyethyl-5,5′-dichloro-oxacarbocyanine was added in an amount of 500 mg per 1 mol of silver), and the dye-donor substance was α, α, α ′, α′-tetrakis [1-phenyl-3-
A similar coating solution was coated on the above except that 0.63 g of isopropanamide-pyrazolin-5-on-4-yl) -m-xylene was used. Furthermore, an intermediate layer consisting of polyvinylpyrrolidone and gelatin was provided (gelatin 0.4 g / m ² ,
Polyvinylpyrrolidone 1.0 g / m ² , provided that 3-methyl-pentane-1,3,5-triol 0.7 g / m ² , 1- (4 (t-butylphenoxy) -3-sulfophenyl) -3-decanamide-4 0.5 g / m ² of-(4-hydroxy-3-sulfophenylazo) -5-one and 0.3 g of 1- (3,5-dicarboxyphenyl) -3- (2-sulfohexadecanamide) pyrazolin-5-one Contains g / m ² . ).

Furthermore, the green-sensitive silver halide emulsion was further converted into a blue-sensitive silver halide emulsion (chemically aged, silver iodogram emulsion, silver iodide content 4 mol%, average grain size 0.15 μm, consisting of cubic grains). Instead, the dye-donor is replaced by α-benzoyl-α- (1
-Phenyl-2- [4- {2-octadecenyl-3-carboxypropanamide} benzyl] -1,2,4-triazolidine-3,5-dione-4-yl) -2-chloro-acetanilide instead of 0.65 g In addition, a similar coating solution was similarly coated on the above. (Comparative Sample 1) Further, the red-sensitive silver halide emulsion was replaced with a grain size of 0.20 μm and a silver iodide content of 4 mol%, and the amount of the photosensitive dye was 300 mg per mol of Ag.
A sample having exactly the same multilayer was prepared, except that the emulsion was reduced to 1. (Comparative Sample 2) Further, a multilayer sample was prepared in the same manner as Comparative Sample 1 except that the coating solution containing the red-sensitive silver halide emulsion was doubled. (Comparative Sample 3) Furthermore, the grains of the infrared silver halide emulsion were directly subjected to the sensitizing dye. Sample 1 was prepared in the same manner as Comparative sample 1 except that the amount added (600 mg / Ag 1 mol) was changed to Sample 1.

Each sample was exposed and developed as described below.

As shown in FIGS. 1 (b) and 1 (c), P-4AA is formed on the fluorescent surface 2 of the fiber plate 1 as shown in FIG. 1 (a).
Fluorescent substance and P22-RE3 fluorescent substance are disclosed in JP-A-58-1202, respectively.
As disclosed in No. 42, using FOT3 (manufactured by Japan Radio Co., Ltd.) having fluorescent screens 2a and 2b which are painted in stripes on the inner surface, P-4AA fluorescent screen 2a with blue and green The Latten filter No. 47B (4a) and the Latten filter No. (4b), which are filters, and the Latten filter No. 26 (4c) pasted on the P22-RE3 fluorescent screen 2b in strips, Use the four types of photosensitive materials 5 as shown in FIG.
Were brought into close contact with the surface of the OFT, and three-color electron beams were scanned for one line at 10 msec while taking respective timings for blue, green, and red signals. The photosensitive material is conveyed by a stepping motor in a direction orthogonal to the scanning direction of the electron beam so that there is almost no space between the photosensitive material and the next scanning line. The OFT creed voltage was changed in the range of 35 to 25 V to change the light emission luminance from 0 to 96 mW / m ^{2 in} 32 steps, and each light-sensitive material was exposed stepwise.

Separately, polyvinyl chloride (n = 1.10
0, manufactured by Wako Pure Chemical Industries, Ltd.) was applied as a tetrahydrofuran solution to prepare an image receiving element so that the dry film thickness of the polyvinyl chloride layer would be 15 μm.

The heat-developable color light-sensitive element and the image-receiving element were superposed and heated at 150 ° C. for 1 minute, and then the image-receiving element was peeled off to obtain a diffusion transfer image. The results are shown in Table 1 below together with the maximum light sensitivity of the panchromatic layer. .

Incidentally, sensitivity, when changing the 32 stage emission in the range of 0~96mW / m ² of OFT, are displayed for the first time images appearing emitting radiation illuminance (mW / m ^2). Therefore, the smaller the value, the higher the sensitivity.

As is clear from Table 1, the sample 1 which is the light-sensitive material of the present invention is used in comparison with the case where the comparative samples 1 to 3 which are the light-sensitive materials having a red-sensitive silver halide other than the present invention are used. If it is, the sensitivity and the maximum density are both excellent. this is,
It is considered that Sample 1 has a good matching with the emission spectrum of the red fluorescent substance P22-RE3 used for the OFT. In Figure 3
The emission spectrum 6 of P22-RE3 and the spectral sensitivities of the panchromatic layers of Comparative Samples 1, 2, 3 and Sample 1 are shown. 7 is comparative sample 1,2
8 of 3 and 3 is a spectral sensitivity curve of the sample 1.

Example 2 As sensitizing dye (Comparative samples 4-6) and Comparative Samples 4, 5 and 6 and Sample 2 were prepared in the same manner as in Example 1 except that (Sample 2) was used.

The results are shown in the table.

As is clear from Table 2, the same results as in Example 1 were obtained using different sensitizing dyes.

Example 3 A as shown below as a sensitizing dye for a red-sensitive silver halide emulsion
Multilayer samples 3 to 6 were prepared in the same manner as in Sample 1 of Example 1 except that B, C and D were used, and three-color exposure of blue, green and red was performed in the same manner as in Example 1. The results are shown in Table 2 below.
Shown in.

It can be seen from Table 3 that both the sensitivity and the maximum density are excellent when the light-sensitive material in which the panchromatic layer containing red-sensitive silver halide has a light-sensitive maximum within the range of the present invention.

Example 4 An experiment was conducted in the same manner as in Example 1 using the same sample as in Example 1 except that the red fluorescent substance of the OFT used in Example 1 was replaced with P27-R2. Essentially similar results to 1 were obtained.

(3) Effects of the Invention In the means for producing a photographic image from an electric image signal, by combining the photosensitive material of the present invention with a CRT as an electro-optical conversion means, both writing efficiency, image quality and operability of image formation are combined. It can be excellent.

For CRT, the light-sensitive material of the present invention has improved writing sensitivity to red as compared with the conventional one, and therefore finer grain silver halide can be used, and therefore thin film can be formed, and dye transfer can be performed. Of the image, and as a result, the maximum density of the image diffused and transferred from the red recording layer is high, and therefore an image having excellent color balance can be obtained from the image electric signal.

[Brief description of drawings]

1 and 2 are used for exposing the light-sensitive material of the present invention.
Explanatory drawing showing an example of a CRT, FIG. 1 (a) is a partially cutaway perspective view of a normal OFT, FIG. 1 (b) is a front view of a fiber plate used in an embodiment, and FIG. 1 (c) is Second view, side view of (b)
The figure shows an explanatory diagram of the exposure state, and FIG. 3 shows the emission spectrum of the red phosphor used in the examples and the spectral sensitivity curve of the photosensitive material. 1 ... Fiber plate, 2 ... Fluorescent surface, 2a ... P-4AA fluorescent screen, 2b ... P22-RE3 fluorescent screen, 3 ... OFT, 4a ... Ratten filter No.47B, 4b ... Ratten filter No. 99, 4c Ratten filter No. 26, 5 ... Photosensitive material, 6 ... Emission spectrum of red fluorescent substance P22-RE3, 7 ... Comparative samples 1 and 2 of Example 1 And spectral sensitivity curves of 3; 8 ... Spectral sensitivity curve of Sample 1 of Example 1.

Claims (1)

[Claims] 1. A photosensitive layer containing, on a support, at least one layer of a blue-sensitive silver halide, an organic silver salt, a dye-donor compound that forms a diffusible yellow dye and a binder, and at least one layer of a green-sensitive halogen. A photosensitive layer containing a silver halide, an organic silver salt, a dye-donor compound that forms a diffusible magenta dye and a binder, and a dye-donor compound that forms at least one layer of a red-sensitive silver halide, an organic silver salt and a diffusible cyan dye. And a photosensitive layer containing a binder,
A heat-developable color diffusion transfer light-sensitive material for CRT, wherein the red-sensitive silver halide has a light-sensitive maximum in the range of 600 to 650 nm.