JPH09292684A - Isothiazolylazophenol dye and color photographic sensitive material utilizing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain a magenta dye excellent in spectral characteristics and high in fastness against light, heat, air, and chemicals, and the like by using a specified phenolic dye. SOLUTION: The color photosensitive material contains the 4-(5-isothiazolyl) azophenol dye represented by the formula and a compound capable of imagewise releasing it. In the formula, each of R<1> -R<4> is, independently, an H atom or a substituent; and each of R<3> and R<4> may combine with each other to form a ring; R<5> is an H or halogen atom or an alkyl, aryl, hetero-cyclic, alkoxy, cyano, alkylthio, or aklylsulfonyl group; and R<6> is a cyano, thiocyano, or carbamoyl group or the like. And these substituents may be substituted by other groups, and when these groups have aliphatic parts, these parts may be straight or branched or cyclic and saturated or unsaturated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 4- (5-isothiazolylazo) phenol dye exhibiting excellent absorption characteristics and having high fastness to light, heat, air, chemicals and the like. It also relates to a color light-sensitive material having an image-forming compound containing a novel 4- (5-isothiazolylazo) phenol dye or a precursor thereof.

[0002]

2. Description of the Related Art Color diffusion transfer photographic methods using azo dye-donor compounds which give azo dyes having a diffusivity different from that of the dye-donor compound as a result of development under basic conditions are well known in the art. ing. For example, as a dye-donating compound that releases a magenta dye, there is disclosed in JP-A-49-
114424, 50-115528, 55-4
No. 028, 61-273542, JP-A-4-331.
954, US. 3,932,380 and 3,932
Those described in No. 1,144 and the like are known. However, the compounds shown in these prior documents still satisfy all of them, because the spectral characteristics of the dye are insufficient and there is a problem in color reproduction, and the fastness to light, heat, air, chemicals, etc. is low. The thing was not found and the improvement was desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a magenta dye having excellent spectral characteristics and having high fastness to light, heat, air, chemicals and the like. Also,
It is an object of the present invention to provide a color light-sensitive material containing a dye-donating compound that has excellent spectral characteristics and releases a magenta dye having high fastness to light, heat, air, chemicals and the like.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have shown that 4- (5-) represented by the following general formula (1).
It has been found that the isothiazolylazo) phenol dye effectively achieves the above-mentioned objects and can sufficiently improve the drawbacks of the prior art.

[0005]

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In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. R ³ and R ⁴ may combine with each other to form a ring structure. R ⁵ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, a cyano group, an alkylthio group or an alkylsulfonyl group. R ⁶ represents a cyano group, a thiocyano group, a nitro group, an alkoxycarbonyl group or a carbamoyl group. Further, these substituents may be further substituted with other substituents.

Further, a color photographic light-sensitive material characterized by containing at least one dye-donor compound represented by the following general formula (2) on a support has sufficiently improved the drawbacks of the prior art. It was found that the objectives of General formula (2) (Dye-X) q-Y In the formula, Dye is the 4- (5-isothiazolylazo) phenol dye represented by the general formula (1) according to claim 1 or its precursor. Represents a dye moiety having three or more, X represents a mere bond or linking group which is cleaved in response to or corresponding to development, and Y corresponds to or inversely corresponds to reaction of a photosensitive silver salt having a latent image on an image. Represents a group having a property of causing a difference in diffusibility of the dye portion. Dye and X are R ¹ , R ² , R ³ of the general formula (1) according to claim 1,
It bonds at at least one of R ⁴ and R ⁵ . q is 1
Or 2, and when q is 2, Dye-X may be the same or different.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. The substituent described in the present invention may be a substitutable group, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic group. Oxy group, aliphatic oxycarbonyl group,
Aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, amino group , Aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, fat Group oxyamino group, aryloxyamino group,
Carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl,
Examples thereof include diaryloxyphosphinyl and the like.

Unless otherwise specified, when a group in the present specification contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic and saturated or unsaturated. May represent, for example, alkyl, alkenyl, cycloalkyl, or cycloalkenyl, which may be unsubstituted or may have a substituent. When an aryl moiety is included, the aryl moiety may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. When it contains a heterocyclic moiety,
The heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring, or a single ring. It may be a condensed ring, may be unsubstituted or may have a substituent.

The general formula (1) will be described in detail below. In R ¹ , R ² , R ³ , and R ⁴ , a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, an alkoxy group, An aryloxy group,
Heterocyclic oxy group, silyloxy group, alkylthio group,
Arylthio group, heterocyclic thio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonamide group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, carbamoylamino group,
A carbamoyloxy group, a sulfamoylamino group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an aryloxycarbonyloxy group, and a sulfonyloxy group are preferable from the viewpoint of the effect of the present invention. More specifically, R ¹ , R ² ,
R ³ and R ⁴ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a carbon number of 12 or less, preferably a carbon number). 8 or less optionally substituted alkyl groups, for example, methyl group, trifluoromethyl group, benzyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, n -Propyl group,
iso-propyl group, n-butyl group, t-butyl group, t
-Pentyl group, cyclopentyl group, n-hexyl group, t
-Hexyl group, cyclohexyl group, y-octyl group, n
-Decyl group, n-undecyl group, n-dodecyl group, etc.), aryl group (C18 or less, preferably C10 or less aryl group which may be substituted. For example, phenyl group, naphthyl group, 3- Hydroxyphenyl group, 3-
Chlorophenyl group, 4-acetylaminophenyl group, 2
-Methanesulfonylphenyl group, 4-methoxyphenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc., heterocyclic group (having 18 or less carbon atoms,
A heterocyclic residue having preferably 10 or less carbon atoms which may be substituted. For example, 1-imidazolyl group, 2-furyl group, 2
-Pyridyl group, 3-pyridyl group, 3,5-dicyano-2
-Pyridyl group, 5-tetrazolyl group, 5-phenyl-1
-Tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazolin-2-yl group, morpholino group, etc., acyl group (having 12 or less carbon atoms, preferably 8 carbon atoms) The following acyl groups which may be substituted, for example, acetyl group, propionyl group, butyroyl group, iso-butyroyl group, 2,2-
Dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3-acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, etc., sulfonyl group (having 12 or less carbon atoms, preferably 8 or less carbon atoms) Optionally a sulfonyl group, for example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-
Octanesulfonyl group, n-dodecanesulfonyl group, benzenesulfonyl group, 4-methylphenylsulfonyl group, etc.),

Alkoxy group (C 12 or less, preferably C 8 or less alkoxy group which may be substituted. For example, methoxy group, ethoxy group, n-propyloxy group,
iso-propyloxy group, cyclohexylmethoxy group, etc.), aryloxy group, heteroaryloxy group (C18 or less, preferably C10 or less, optionally substituted aryloxy or heteroaryloxy group, for example, phenoxy. Group, naphthyloxy group, 4-acetylaminophenoxy group, pyrimidin-2-yloxy group, 2-pyridyloxy group, etc.), silyloxy group (having 10 or less carbon atoms, preferably 7 or less carbon atoms and optionally substituted silyloxy) Group, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, etc., alkylthio group (C12 or less, preferably C8 or less, optionally substituted alkylthio group. For example, methylthio group, ethylthio group, n -Butylthio group,
n-octylthio group, t-octylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-hydroxyethylthio group, etc.), arylthio group, heterocyclic thio group (C18 or less, preferably substituted with C10 or less) Also, an arylthio group and a heteroarylthio group.
For example, a phenylthio group, a 4-chlorophenylthio group,
2-n-butoxy-5-t-octylphenylthio group,
4-nitrophenylthio group, 2-nitrophenylthio group, 4-acetylaminophenylthio group, 1-phenyl-5-tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-yl group, etc., carbamoyl group (carbon number) An optionally substituted carbamoyl group having 12 or less, preferably 8 or less carbon atoms, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2
-Methoxyethyl) carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n-octylcarbamoyl group, etc., sulfamoyl group (C12 or less, preferably C8 or less optionally substituted sulfamoyl group, for example, Sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, bis-
(2-methoxyethyl) sulfamoyl group, diethylsulfamoyl group, di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N -Methylsulfamoyl group),

Acylamino group (C12 or less, preferably C8 or less, optionally substituted acylamino group.
For example, an acetylamino group, a 2-carboxybenzoylamino group, a 3-nitrobenzoylamino group, a 3-diethylaminopropanoylamino group, an acryloylamino group, etc., a sulfonylamino group (having 12 or less carbon atoms, preferably having 8 or less carbon atoms) A sulfonylamino group which may be substituted, for example, a methanesulfonylamino group, a benzenesulfonylamino group, a 2-methoxy-5-n-methylbenzenesulfonylamino group, an alkoxycarbonylamino group (having 12 or less carbon atoms, preferably An alkoxycarbonylamino group which may be substituted by the number 8 or less, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a 2-methoxyethoxycarbonylamino group,
an iso-butoxycarbonylamino group, a benzyloxycarbonylamino group, a t-butoxycarbonylamino group, a 2-cyanoethoxycarbonylamino group, or the like; an alkoxycarbonyloxy group (having 12 or less carbon atoms, preferably 8 or less carbon atoms) An alkoxycarbonyloxy group such as a methoxycarbonyloxy group,
An ethoxycarbonyloxy group, a methoxyethoxycarbonyloxy group, etc., an aryloxycarbonylamino group (having 12 or less carbon atoms, preferably 8 or less carbon atoms, which may be substituted), for example, a phenoxycarbonylamino group, 2 , 4-nitrophenoxycarbonylamino group, 4-t-butoxyphenoxycarbonylamino group and the like, carbamoylamino group (C 12 or less, preferably C 8 or less carbamoylamino group which may be substituted. For example, methylamino Carbonylamino group, morpholino carbonylamino group,
Diethylaminocarbonylamino group, N-ethyl-N-
Phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, 4-methanesulfonylaminocarbonylamino group, etc., carbamoyloxy group (C12 or less, preferably C8 or less carbamoyloxy group which may be substituted) For example, dimethylaminocarbonyloxy group, pyrrolidinocarbonyloxy group, etc., sulfamoylamino group (having 12 or less carbon atoms, preferably 8 or less carbon atoms, optionally substituted sulfamoylamino group. Amino group, di-n-butylaminosulfonylamino group, phenylaminosulfonylamino group, etc.),

Amino group (C12 or less, preferably 8)
The following optionally substituted amino groups. For example, an amino group,
Methylamino group, dimethylamino group, ethylamino group,
Ethyl-3-carboxypropylamino group, ethyl-2
-A sulfoethylamino group, a phenylamino group, a methylphenylamino group, a methyloctylamino group, etc., an alkoxycarbonyl group (an optionally substituted alkoxycarbonyl group having 10 or less, preferably 6 or less carbon atoms, for example, methoxycarbonyl) Group, ethoxycarbonyl group,
A methoxyethoxycarbonyl group, etc.), an aryloxycarbonyl group (an optionally substituted aryloxycarbonyl group having 15 or less, preferably 10 or less carbon atoms, such as a phenoxycarbonyl group, a p-methoxyphenoxycarbonyl group, etc.), an acyloxy group (C 12 or less, preferably 8 or less, optionally substituted acyloxy group. For example, acetoxy group, benzoyloxy group, 2-
Butenoyloxy group, 2-methylpropanoyloxy group, etc., aryloxycarbonyloxy group (C 1
2 or less, preferably 8 or less optionally substituted aryloxycarbonyloxy groups. For example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group, 4
-T-butoxycarbonylaminophenoxycarbonyloxy group, etc., sulfonyloxy group (having 12 or less carbon atoms, preferably 8 or less sulfonyloxy group which may be substituted. For example, phenylsulfonyloxy group, methanesulfonyloxy group, chloromethane It is preferably a sulfonyloxy group, a 4-chlorophenylsulfonyloxy group, a dodecylsulfonyloxy group or the like).

Of these, a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, a sulfonamide group, a carbamoyl group, a cyano group, an alkoxy group and a carbamoylamino group are more preferable, and these substituents other than the hydrogen atom are preferable. It is more preferable that any of the above is substituted with R ¹ .

Most preferably, R ¹ is a halogen atom, an acylamino group, a carbamoyl group or a cyano group.

R ⁵ is a hydrogen atom, an alkyl group (having 12 carbon atoms
Hereafter, an alkyl group which preferably has 8 or less carbon atoms and may be substituted, for example, a methyl group, a trifluoromethyl group, an acetylaminomethyl group, an ethyl group, a carboxyethyl group, an allyl group, an n-propyl group, and iso-propyl Group,
n-butyl group, t-butyl group, t-pentyl group, cyclopentyl group, n-hexyl group, t-hexyl group, cyclohexyl group, t-octyl group, n-decyl group, etc.),
Preferably, an aryl group such as a chlorine atom or a bromine atom (an optionally substituted aryl group having 18 or less carbon atoms, preferably 10 or less carbon atoms, for example, a phenyl group, a naphthyl group, 3
-Hydroxyphenyl group, 3-chlorophenyl group, 4-
Acetylaminophenyl group, 2-methanesulfonylphenyl group, 4-methoxyphenyl group, 2,4-dimethylphenyl group, etc., heterocyclic group (having 18 or less carbon atoms, preferably 10 or less carbon atoms may be substituted). A heterocyclic group,
For example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 2-thienyl group, etc., alkoxy group (C 12 or less, preferably 8 or less, optionally substituted alkyl group, for example, methoxy group , Ethoxy group, i-propyl group, methoxyethoxy group and the like), cyano group, alkylthio group (C12 or less, preferably C8 or less alkylthio group, for example, methylthio group, ethylthio group, n-butylthio group, benzylthio group. Group) and an alkylsulfonyl group (an alkylsulfonyl group having 12 or less, preferably 8 or less carbon atoms, such as a methanesulfonyl group or a butanesulfonyl group). Preferred among these are a hydrogen atom and an alkyl group.

R ⁶ is a cyano group, a nitro group, a thiocyano group, an alkoxycarbonyl group (an alkoxycarbonyl group having a carbon number of 10 or less, preferably 6 or less, which may be substituted, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a methoxyethoxy group. Carbonyl group, etc., carbamoyl group (C12 or less, preferably C8 or less, optionally substituted carbamoyl group, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group, etc. ) Is represented. Preferred among these is a cyano group.

The dye in which R ³ and R ⁴ are bonded to each other to form a ring structure is represented by the following general formula (3) or (4).

[0019]

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In the formula, R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as defined in the general formula (1), and R ⁸ , R ⁹ and R 6
¹⁰ , R ¹¹ has the same definition as R ^{1 in} the general formula (1), and R
¹² is a hydrogen atom or an alkyl group (having 12 or less carbon atoms). Q represents an atomic group necessary for forming a 5- to 7-membered ring.

The dye of the general formula (3) is preferably as follows. R ¹ is a hydrogen atom, an acylamino group (having 2 to 12 carbon atoms), a sulfamoyl group (having 1 to 12 carbon atoms),
A carbamoyl group (having 2 to 12 carbon atoms) and a sulfonamide group (having 1 to 12 carbon atoms), R ² is a hydrogen atom, R ⁸ and R
¹¹ is a hydrogen atom, a sulfonamide group (having 1 to 1 carbon atoms
2), an acylamino group (having 2 to 12 carbon atoms), an alkoxycarbonylamino group (having 2 to 12 carbon atoms), R ⁸ ,
R ¹⁰ is a hydrogen atom. R ⁵ and R ⁶ are the same as the preferred substituents mentioned in the general formula (1).

The dye of the general formula (4) is preferably the following:
It is as follows. R¹Represents a hydrogen atom, an acylamino group (carbon
2-12) and R^TwoIs a hydrogen atom, R¹²Is water
And Q is -C (R¹³) (R¹⁴)-Or-
C (R ¹³) (R¹⁴) -C (R^Fifteen) (R¹⁶)-And R
¹³, R¹⁴, R^Fifteen, R¹⁶Is a hydrogen atom or an alkyl group (charcoal
Prime numbers 1 to 6).

Isothia represented by the general formula (1) of the present invention
Among the zolylazo dyes, in terms of the effect of the present invention, R¹Is halo
Gen atom, alkyl group, acylamino group, sulfonami
Group, carbamoyl group, cyano group, alkoxy group, cal
A vamoylamino group, wherein R^FiveIs an alkyl group
And R⁶Is more preferably a cyano group,
¹Is a halogen atom, an acylamino group, a carbamoyl group,
A cyano group, R^FiveIs a methyl group and R⁶Is
Most preferred is an ano group.

When the dye of the present invention is used in the diffusion transfer image forming method, it is used as a dye-donor compound described below. General formula (2) (Dye-X) q-Y In the formula, Dye is the 4- (5-isothiazolylazo) phenol dye represented by the general formula (1) according to claim 1 or its precursor. Represents a dye moiety having three or more, X represents a mere bond or linking group which is cleaved in response to or corresponding to development, and Y corresponds to or inversely corresponds to reaction of a photosensitive silver salt having a latent image on an image. Represents a group having a property of causing a difference in diffusibility of the dye portion. Dye and X are R ¹ , R ² , R ³ of the general formula (1) according to claim 1,
It bonds at at least one of R ⁴ and R ⁵ . q is 1
Or 2, and when q is 2, Dye-X may be the same or different.

The details of the compound of the general formula (2) are described below.
Will be described. q is 1 or 2, and when q is 2, Dy
e-X may be the same or different, but is preferable.
Q is 1. Dye and X are the above-mentioned general formula (1).
R ¹, R^Two, R^Three, R^Four, R^FiveTo at least one of
And combine. As a precursor of the dye represented by Dye
Examples of dyes include dyes that have generally been absorption-shifted.
No. 4,310,612.
No. 3,579,334, and JP-A-57-15.
No. 8,638.

Basically, X may be bonded to any site of the Dye portion, and the linking group represented by X is --N (R ¹⁷ )-.
(R ¹⁷ represents a hydrogen atom, an alkyl group or a substituted alkyl group), —SO ₂ —, —CO—, an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group. , -O-,
-SO- and groups obtained by combining two or more of these divalent residues are typical examples, of which -N is preferable.
_{^{R 17 -SO 2 -, - NR}} 17 -CO- or -R ¹⁸ - (L) _k
A group represented by — (R ¹⁹ ) _p —, R ¹⁸ and R
¹⁹ represents an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group, respectively, L is -O-, -CO-, -SO-, -S
_{O 2 -, - SO 2 NH} -, - NHSO 2 -, - CONH
Represents-, -NHCO-, k represents 0 or 1, and p represents 1 or 0. Also, -NR ¹⁷ -SO _2-
And -NR ¹⁷ -CO- and _{^{-R 18 - (L) k -}} (R 19) p -
A combination of and is also preferable. Bonding mode of Dye portion and Y portion is particularly preferably of the form of Dye-SO ₂ NH-Y.

Next, Y will be described. Y represents a group capable of cleaving a YX bond corresponding to or inversely corresponding to photosensitive silver halide having a latent image. Such groups are known in the field of photographic chemistry utilizing diffusion transfer of dyes, and are described, for example, in U.S. Pat.
No. 184852).

The Y will be described in detail. The expression was described including X. (1) As Y, a negative-acting releaser that first releases a photographically useful group in response to development is exemplified.

As Y classified into the negative-acting releaser, a releaser group releasing a photographically useful group from an oxidant is known. Preferred examples of this type of Y include the following formula (Y-1). Formula (Y-1)

[0030]

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Where β is necessary to form a benzene ring
Represents a group of non-metallic atoms.
An unsaturated carbocycle or heterocycle may be condensed. α is-
OZ ^TwoOr -NHZ^ThreeWhere Z^TwoIs a hydrogen atom
Or a group which forms a hydroxyl group by hydrolysis;
^ThreeRepresents a hydrogen atom, an alkyl group, an aryl group, or
Represents a group that produces an amino group when dissolved. Z¹Is a substituent
Alkyl group, aryl group, aralkyl
Group, alkoxy group, alkylthio group, aryloxy
Group, arylthio group, acyl group, sulfonyl group, acyl
Amino group, sulfonylamino group, carbamoyl group, sulfo
Famoyl group, ureido group, urethane group, heterocyclic group
Or a cyano group or a halogen atom, and a represents a positive integer.
Shi Z¹Are different even if they are the same when
May be. For formula (Y-1), -X is -NHS
O_TwoZ^FourA group represented by^FourRepresents a divalent group.

Among the groups contained in the formula (Y-1), a preferable group is the formula (Y-2) or the formula (Y-3). Formula (Y-2)

[0033]

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Formula (Y-3)

[0035]

[Chemical 6]

In the formula, Z ² and X have the same meaning as described in formula (Y-1). Z ⁵ and Z ⁶ represent an alkyl group, an aryl group or an aralkyl group, and these may have a substituent. Further, Z ⁵ is a secondary or tertiary alkyl group, and it is preferable that the sum of the carbon numbers of Z ⁵ and Z ⁶ is 20 or more and 50 or less.

Specific examples of these are shown in US Pat. No. 4,055,4.
28, 4,336,322, JP-A-51-113.
No. 624, No. 56-16131, No. 56-71061
No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, No. 57-40
No. 43, No. 59-60439, JP-B-56-1765
No. 6 and No. 60-25780.

Another example of Y is formula (Y-4). Formula (Y-4)

[0039]

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In the formula, α, Y, Z ¹ and a have the same meanings as described in the formula (Y-1). β'represents a group of non-metal atoms necessary to form a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle.

In the group represented by the formula (Y-4), α is -O.
Z ² in which β ′ forms a naphthalene skeleton is preferred. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

Further, as a releaser releasing a photographically useful group by the same reaction as in the formulas (Y-1) and (Y-2), JP-A-51-104343 and JP-A-53-46730,
54-130122, 57-85055, 5
No. 3-3819, No. 54-48534, No. 49-64.
No. 436, No. 57-20735, Japanese Patent Publication No. 48-321
29, 48-39165, U.S. Pat.
The groups described in No. 934 are mentioned.

The compound releasing the photographically useful group from the oxidant by another reaction mechanism is represented by the formula (Y-5) or the formula (Y
The hydroquinone derivative represented by -6) is mentioned. Formula (Y-5)

[0044]

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Formula (Y-6)

[0046]

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Where β'is Z in the formula (Y-4).^TwoIs the formula (Y-
It has the same meaning as described in 1), and Z⁷Is Z^TwoIs synonymous with
Z⁸Is Z¹Represents a substituent or a hydrogen atom described above. Z^Two
Is Z ⁷May be the same or different. This kind of
Specific examples are described in US Pat. No. 3,725,062.
You.

Examples of this type of hydroquinone derivative releaser having a nucleophilic group in the molecule are also included. Specifically, it is described in JP-A-4-97347.

Another example of Y is US Pat. No. 3,44.
P-hydroxydiphenylamine derivatives described in U.S. Pat. No. 3,939, U.S. Pat. Nos. 3,844,785 and 4,684,604; D. And hydrazine derivatives described in Journal No. 128, p. 22.

Further, examples of the negative acting releaser include the following formula (Y-7). Formula (Y-7)

[0051]

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In the formula, Coup represents a group capable of coupling with an oxidized product of p-phenylenediamines and p-aminophenols, that is, a group known as a photographic coupler. A specific example is described in British Patent 1,330,524.

(2) Next, examples of Y include a positive-working releaser which releases a photographically useful group in the opposite manner to development.

Examples of the positive-acting releaser include a releaser that exhibits a function when reduced during treatment. Preferred examples of this type of Y include the following formula (Y-
8). Formula (Y-8)

[0055]

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In the formula, EAG represents a group that receives an electron from a reducing substance. N represents a nitrogen atom, W is an oxygen atom, a sulfur atom or -NZ ¹¹ - represents the EAG is the N-W bond is cleaved after receiving electrons. Z ¹¹ represents an alkyl group or an aryl group. Z ⁹ and Z ^{10 each} represent a mere bond or a substituent other than a hydrogen atom. A solid line indicates a bond, and a broken line indicates that at least one of them is connected.

Among the groups represented by the formula (Y-8), the preferred one is the formula (Y-9). Formula (Y-9)

[0058]

[Chemical 12]

In the formula, O represents an oxygen atom (that is, the formula (Y-
8) W is an oxygen atom), Z ¹² forms a heterocycle containing an N—O bond, and Z ¹² − is formed following the cleavage of the N—O bond.
Represents an atomic group having the property of breaking an X bond. Z ¹² may have a substituent or a saturated or unsaturated ring may be condensed. Z ¹³ represents -CO- or -SO ₂ -
Represents

A more preferred group of formula (Y-9) is formula (Y-10). Formula (Y-10)

[0061]

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In the formula, Z ¹⁴ represents an alkyl group, an aryl group or an aralkyl group, Z ¹⁵ represents a carbamoyl group or a sulfamoyl group, Z ¹⁶ represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group or an aryloxy group. Represents a group, an arylthio group, a halogen atom, a cyano group, and a nitro group, and b represents an integer of 0 to 3. The substitution position of the nitro group in the formula is ortho or para to the nitrogen atom. It is most preferable that Z ¹⁵ is a carbamoyl group or a sulfamoyl group substituted with an alkyl group having 12 to 30 carbon atoms.

A specific example of this type of Y is disclosed in JP-A-62-2.
No. 15,270 and U.S. Pat. No. 4,783,396.

As another positive-acting releaser which exhibits a reduced function, BEND compounds described in US Pat. Nos. 4,139,379 and 4,139,389, and British Patent 11,445. Listed in Carq
uin compound, JP-A-54-126535, JP-A-57.
-84453.

When these reducible releasers represented by Y represented by formula (Y-8) are used, a reducing agent is used in combination, but L containing a reducing group in the same molecule is used.
DA compounds are also included. This is US Pat. No. 4,551,
No. 423.

There is also a type of positive-working releaser which is incorporated as a reductant in a light-sensitive material and deactivates when oxidized during processing. Japanese Patent Application Laid-Open No. 51-63618 and U.S. Pat.
Fields compound described in No. 79 and JP-A-49-11162
No. 8, No. 52-4819, U.S. Pat. No. 4,199,35
The Hinshaw compounds described in No. 4 are mentioned.

As an example of Y of this type, the formula (Y-11)
Can also be mentioned. Formula (Y-11)

[0068]

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Z in the formula¹⁷, Z¹⁹Is a hydrogen atom or
Or unsubstituted acyl group, alkoxycarbonyl group, ari
Represents an aryloxycarbonyl group, Z¹⁸Is an alkyl group,
Reel group, aralkyl group, acyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
A sulfonyl group, a sulfonyl group or a sulfamoyl group;²⁰, Z
^{twenty one}Is a hydrogen atom or a substituted or unsubstituted alkyl group,
Represents a reel group or an aralkyl group. Specifically, JP-A-62
-245270 and 63-46450.
You.

A thiazolidine type releaser may be mentioned as a positive-acting releaser having another mechanism. Specifically, U.S. Pat. No. 4,468,451, and JP-A-7-1599
62.

Specific examples of the dye of the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto.

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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Specific examples of the dye-donating compound of the general formula (2) used in the present invention are shown below, but the present invention is not limited thereto.

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[0079]

[Chemical 21]

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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Hydrophobic additives such as the above-mentioned dye-providing compounds and image-forming accelerators described below are described in US Pat.
It can be incorporated into the layer of the photosensitive element by a known method such as the method described in No. 322,027. In this case,
JP-A-59-83154, JP-A-59-178451,
59-178452, 59-178453, 59-178454, 59-178455, 5
The high boiling point organic solvent as described in 9-178457 and the like can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-donating compound used. In addition, Japanese Patent Publication 51-39
The dispersion method using a polymer described in JP-A-853 and JP-A-51-59943 can also be used.

In the case of a compound that is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When the hydrophobic substance is dispersed in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636 (37) to (3)
8) The surfactants listed on the page can be used.

In the present invention, a dye donating compound represented by the following general formula (5) can be used in combination. General formula (5) DYE-Y

Here, DYE represents a dye or its precursor, and Y represents a component which gives a compound having a different diffusibility from the compound under alkaline conditions. According to the function of Y, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion.

Specific examples of the negative type Y include those which are oxidized as a result of development and cleaved to release a diffusible dye.

A specific example of Y is disclosed in JP-A-2-32335, page (15), upper right column, line 18 to the same, page (15), lower left column 2,
This is described in U.S. Pat. No. 3,928,312 described in the 0th line.

Among Y of the negative dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). it can. Representative examples of Y, positive-type compounds, and other types of compounds are described in JP-A-2-32335, page (16), upper left column to JP-A-2004-32335 (1).
7) The contents of the description up to the 7th line in the lower right column of the page apply.

When the dye-donor compound that can be used in the present invention is a reducible dye-donor compound, a reducing agent (also referred to as an electron donor) is used. The reducing agent may be supplied from the outside or may be contained in the light-sensitive material in advance. Further, a reducing agent precursor which has no reducing property itself but exhibits a reducing property by the action of a nucleophile or heat in the developing process can also be used.

Examples of the electron donor used in the present invention include 49-50 of US Pat. No. 4,500,626.
Column, column Nos. 30-31 of No. 4,483,914;
330,617, 4,590,152, JP-A-6
0-140335, pages (17) to (18), ibid.
No.-40245, No.56-138736, No.59-1
No. 78458, No. 59-53831, No. 59-182
No. 449, No. 59-182450, No. 60-1195
No. 55, 60-128436 to 60-1284
No. 39, No. 60-198540, No. 60-181
No. 742, No. 61-259253, No. 62-2440
No. 44, No. 62-131253 to No. 62-1312
No. 56, No. 78 of EP 220,746 A2.
And electron donor precursors described on pages 96 to 96 and the like. Various electron donor combinations, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When the dye-donor compound of the present invention is diffusion resistant, or when the reducing agent used in combination with the reducible dye-donor compound of the present invention is diffusion resistant, an electron transfer agent is used. Is also good.

The electron transfer agent or its precursor can be selected from the above-mentioned electron donors or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion-resistant electron donor. Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant electron donor used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the above-mentioned reducing agents, and preferably hydroquinones and sulfonamidephenols. , Sulfonamide naphthols, and compounds described as electron donors in JP-A No. 53-110827. The electron transfer agent may be supplied from the outside or may be contained in the light-sensitive material in advance.

The dye-donor compounds that can be used in the present invention are
It is preferably contained in the same layer as the photosensitive silver halide emulsion, but may be contained in any layer as long as it can react directly or via an electron transfer agent. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion layer, a decrease in sensitivity can be prevented. In the present invention, the dye-donating compound can be used in a wide range of amounts and is used in an amount of 0.01 to 5 mol, preferably 0.05 to 1 mol, per 1 mol of silver.

The image-forming compound of the present invention can be used in a diffusion transfer type color photographic light-sensitive material. The developing / image-forming method is to develop the processing composition at room temperature or to supply a trace amount of water or to use a thermal solvent. It is possible to employ a method in which the heat development is carried out by incorporating the above.

First, the color diffusion transfer method will be described. A typical form of the film unit used in the color diffusion transfer method is that an image receiving element (dye fixing element) and a photosensitive element are laminated on one transparent support, and after the transfer image is completed, the photosensitive element is removed. This is a form that does not need to be separated from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred form of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-donor substance for each emulsion layer, A combination of a magenta dye-donating substance and a cyan dye-donating substance (herein, "infrared light-sensitive emulsion layer" means an emulsion layer sensitive to light of 700 nm or more, especially 740 nm or more). ). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the layer containing the dye-providing substance so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled off from the image receiving element.
7840 and Canadian Patent 674,082).

In another embodiment of the laminate type which is peelable, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, and (a) on a white support described in JP-A-63-226649. c) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming substance, an alkali processing composition containing a light-shielding agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit characterized by having a layer having a light shielding function on the side opposite to the side where the processing composition is developed.

In another form in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,71.
No. 8 is described.

On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. Before the end of the exposure, the photosensitive layer-coated surface and the mordant layer-coated surface are not opposed to each other, but after the end of the exposure (for example, during the developing process), the photosensitive layer-coated surface is turned upside down and overlaps with the image-receiving layer-coated surface. .
After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. However, the photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

A pressure rupturable container (processing element) containing an alkaline processing liquid may be combined with the above-mentioned form. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes with pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

The image receiving element of the color diffusion transfer method will be described in more detail below. The image receiving element of the color diffusion transfer method preferably has at least one layer containing a mordant (mordanting layer). As the mordant, those known in the field of photography can be used. A specific example is British Patent 2,011.
1,912, 2,056,101, 2,09
No. 3,041, U.S. Pat. Nos. 4,115,124, 4,273,853, 4,282,305, JP-A-59-232340, JP-A-60-118834, and JP-A-60-128443. No. 60-122940, No. 6
Nos. 0-122921 and 60-235134.

In addition to the above, various additives may be appropriately used in the image receiving element for the color diffusion transfer method, and regarding this, the item of the dye fixing element (image receiving element) for the color diffusion transfer method for heat development can be used. Will be explained together.

Next, the photosensitive element of the color diffusion transfer method will be described. Japanese Patent Application Laid-Open No. 2-32335 discloses a processing composition such as a silver halide emulsion, a spectral sensitizing dye, an emulsion layer, and a full-color multilayer structure used in a color diffusion transfer method. 17) Bottom right column, line 8 to the same publication (20) Bottom right column 19
The contents described up to the line apply.

Next, the peeling layer of the color diffusion transfer method will be described. The release layer used in the present invention can be provided at any place on the photosensitive sheet in the unit after processing. Examples of the release material include JP-A-47-8237, JP-A-59-220727, JP-A-49-4653, U.S. Pat. Nos. 3,220,835, 4,359,518, and JP-A-49-49518. No.-4334, No.50-65133, No.45
-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746, and 4,366,227 can be used. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. In addition, there are various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins, for example, acetylated gelatin, phthalated gelatin and the like can be used. Further, polyvinyl alcohol, polyacrylate, polymethyl methacrylate or a copolymer thereof is used. Of these, a cellulose derivative is preferably used as the release material, and hydroxyethyl cellulose is particularly preferably used. In addition to the water-soluble cellulose derivative, a granular substance such as an organic polymer can be used as a material for peeling. The organic polymer used in the present invention has an average particle size of 0.0
Polymer latexes such as polyethylene, polystyrene, polymethyl methacrylate, polyvinylpyrrolidone, butyl acrylate, and the like having a size of 1 μm to 10 μm are mentioned. Here, as described below, air is contained inside, and the outside is made of an organic polymer. It is preferable to use a light-reflective hollow polymer latex containing a material. The light-reflective hollow polymer latex is disclosed in JP-A-61-1516.
The compound can be synthesized by the method described in No. 46.

Next, the heat development color diffusion transfer method will be described. The heat-developable color light-sensitive material of the present invention basically contains a reducing agent, a binder and a dye-donating compound on a support, and may further contain an organic metal salt oxidizing agent and the like, if necessary. . These components are often added to the same layer, but may be added separately to another layer if they can react. For example, when the colored reducible dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The electron donor is preferably incorporated in the photothermographic material, but may be supplied externally by, for example, diffusing it from a dye fixing element described below.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, it is necessary to combine at least three silver halide emulsion layers each having a different spectral region with a photosensitive silver halide emulsion layer. To use. For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of three layers of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. The order of arrangement of the respective photosensitive layers is arbitrary, and various arrangement orders known for ordinary type color photosensitive materials can be adopted. Further, each of these photosensitive layers may be divided into two or more layers as necessary, as described in JP-A-1-252954. Photothermographic materials include protective layers, undercoat layers, intermediate layers,
Various auxiliary layers such as a yellow filter layer, an antihalation layer, and a back layer can be provided. Specifically, an undercoat layer as described in U.S. Pat. No. 5,051,335, JP-A-1-167,838, JP-A-61-20,943.
Intermediate layer having a solid pigment as described in JP-A No.
20,553, 5-34,884, 2-64,
No. 634, US Pat. No. 5,017,454, US Pat.
9,919 and JP-A-2-235,044, an intermediate layer having an electron transfer agent, JP-A-4-249,24.
A protective layer having a reducing agent as described in No. 5 or a layer obtained by combining them can be provided. The protective layer is preferably divided into two layers. In the case of photothermographic materials, it is often necessary to add various additives to the protective layer, so that the film strength is weakened and the film is easily scratched. Therefore, it is preferable to divide the protective layer into two layers and to make the uppermost layer a binder-rich composition while keeping the amount of additives (particularly oil-soluble components) added to the binder low from the viewpoint of increasing the film strength. When the support is polyethylene-laminated paper containing a white pigment such as titanium oxide, the back layer has an antistatic function and a surface resistivity of 10 ¹² Ω · cm.
It is preferable that the design is made as follows.

The silver halide emulsion (emulsion containing photosensitive silver halide) used in the present invention may have various shapes. Examples thereof include regular particles having regular crystals such as cubes, octahedra and tetradecahedrons, tabular grains, spherical grains, grains having irregular crystal forms such as potato grains, etc. Can be raised. The photosensitive silver halide that can be used in each photosensitive layer of the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. The silver halide emulsion may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. In particular, a method of mixing emulsions having different sensitivities for adjusting gradation (for example, JP-A-1-167744) is preferably used. Particle size is 0.1-2 μm, especially 0.2-1.5
μm is preferred. The photosensitive silver halide emulsion used in the present invention is preferably a core-shell emulsion. In addition, Japanese Patent Laid-Open No. 3-1
A monodisperse emulsion having a coefficient of variation of 20% or less described in 10555 is preferable. Specifically, US Pat. No. 4,50
0,626 No. 50, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 3
6544 (1994), JP-A-62-253159.
No. 3-110555 and 2-236546.
No. 1, No. 1-167743, No. 6-332,093,
Any of the silver halide emulsions described in 6-301,129, 6-230,491, 6-194,768, 6-194,766, European Patent 618,484A and the like. You can use peach.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, JP-A-2-236542, JP-A-1-116637, and JP-A-6-116637
258,755, 6-235,992, Japanese Patent Application No. 4
The emulsion described in JP-A-126629 or the like is preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thioether compound or JP-B No. 47-1 is used as a silver halide solvent.
Organic thioether derivatives described in 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

For other conditions, see P. Graphide, "Shimmie Physic Photographic".
[Paul Montel, 1967], G. Duffin, "Photographic Emulsion Chemistry" (published by The Focal Press, 1966).
Year ", Bier Zerikman et al.," Making and Coating Photographic Emulsion "(published by The Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-5-142329).
No. 5-158124, U.S. Pat. No. 3,650,575).
Further, the method of stirring the reaction solution may be any known stirring method. The temperature of the reaction solution during the formation of silver halide grains,
The pH may be set as desired for any purpose. The preferred pH range is 2.2-7.0, more preferably 2.5
Is about 6.0.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. The chemical sensitization of the light-sensitive silver halide emulsion of the present invention may be performed by a known method such as a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method and a selenium sensitization method alone or in combination with an emulsion for a conventional light-sensitive material. (For example, JP-A-3-110555 and Japanese Patent Application No. 4-75).
798). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-2531).
59). The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

The additives used in such steps and the known photographic additives usable in the invention are described in RD No. 3 above.
6,554, the same No. 18,716 and the same No. 307,1
05 and the corresponding portions are summarized in the following table. Type of additive RD36544 RD18716 RD307105 Chemical sensitizers 510 to 511 pages 648 pages right column 866 pages 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer 511 to 514 page 648 page right column 866 to 868 supersensitizer to page 649 right column 4. Whitening agent 514 pages 648 pages right column 868 pages 5. Antifogging agent 515-517 page 649 page right column 868-870 page stabilizer 6. Light absorbers 517 to 518 pages 649 right column page 873 filter dyes to 650 left column ultraviolet absorbers 7. Dye image stabilizer page 527 page 650 page left column page 872 8. Hardener 508 page 651 page left column 874 to 875 page 9. Binder 507 pages 651 pages left column 873 to 874 pages 10. Plasticizer page 519 page 650 page right column page 876 lubricant 11. Coating aid, page 519, page 650, right column, pages 875 to 876, surfactant 12. Static 520 pages 650 pages right column 876 to 877 inhibitors 13. Matting agent 521 pages 878 to 879 pages

Gelatin is advantageously used as a protective colloid used in the preparation of the light-sensitive silver halide emulsion of the present invention and as a binder for the constituent layers of other light-sensitive materials and dye-fixing elements, but other hydrophilic substances are used. Binders can also be used. Examples thereof include Research Disclosure mentioned above and JP-A-64-13,54.
Examples thereof include those described in No. 6, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include proteins such as gelatin and gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol. , Polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Further, superabsorbent polymers described in JP-A-62-245260 and the like, that is, -COOM or-
A homopolymer of a vinyl monomer having SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate,
Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable.Depending on various purposes, lime-processed gelatin, acid-processed gelatin, demineralized gelatin with a reduced content of calcium, etc., and oxidized to reduce methionine residues according to various purposes. It may be selected from gelatin and the like, and it is also preferable to use them in combination.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Further, when a superabsorbent polymer, polyvinyl alcohol, or a polysaccharide is used in the dye fixing layer or its protective layer as described in Japanese Patent Application No. 5-181,413, the dye may be removed from the dye fixing element after transfer. It is possible to prevent the retransfer to the thing. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less,
Further, it is appropriate that the weight be 7 g or less.

A constituent layer (including a back layer) of a light-sensitive material or a dye-fixing element is used for the purpose of improving physical properties of a film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. Especially,
When a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, a curl preventing effect can be obtained. .

In the present invention, a development inhibitor releasing redox compound can be used. For example, JP-A-61-21
3,847, 62-260,153, JP-A-2-
68,547, 2-110,557, 2-25
Those described in Nos. 3,253 and 1-150,135 can be used. The synthesis method of the development inhibitor releasing redox compound used in the present invention is described in, for example, JP-A-61-
213,847, 62-260,153, U.S. Pat. No. 4,684,604, JP-A-1-269936.
Nos. 3,379,529 and 3,620,
746, 4,377,634, 4,332,8
No. 78, JP-A-49-129,536 and JP-A-56-15
3,336, 56-153,342 and the like.

The development inhibitor releasing redox compound of the present invention contains 1 × 10 ^{−6 to} 5 × 10 ⁻² per mol of silver halide.
Mole, more preferably in the range of 1 × 10 ^-5 to 1 × 10 ^-2 mole. The development inhibitor releasing redox compound used in the present invention may be any suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. And methylcellosolve. In addition, 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. Objects can also be created and used. Alternatively, by a method known as a solid dispersion method, a powder of a development inhibitor-releasing redox compound is placed in water with a ball mill, a colloid mill,
Alternatively, they can be used by being dispersed by ultrasonic waves.

Further, the development inhibitor releasing redox compound may be used in combination with a releasing aid. For example, those described in JP-A-3-293666 can be used.

When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (38)
The surfactants listed on the page can be used.
In the present invention, a compound which activates the development of the photosensitive material and simultaneously stabilizes the image can be used. Specific compounds preferably used are described in U.S. Pat.
No. 0,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. The relationship between the photosensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer described in US Pat. No. 4,500,626, column 57, can be applied to the present invention. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat.
00,626, columns 58-59 and JP-A-61-8825.
No. 6, pages (32) to (41);
Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting polymer compound as described in JP-A-63,079 may be used. The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. Specifically, Japanese Patent Application Laid-Open No. 62-253159 (2)
5), pages 62-245253 and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) are effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
Nos. 6641 and 61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
There are compounds described in JP-A-62-174741, JP-A-61-88256 (pages 27-29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
No. 5272, pages (125) to (137). The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing material in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive material. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other. A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, whether the dye-fixing element contains a fluorescent whitening agent,
It is preferable to supply from the outside such as a photosensitive material. As an example, K.K. Edited by Weenkataraman "Th
e Chemistry of Synthetic
Dyes, Vol. V, Chapter 8, JP-A-61-143752, and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 4 can be used.
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157). Particularly preferred is JP-A-Hei 3
The vinyl sulfone type hardener described in -114041 is used.

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457. The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 944, No. 62-135826 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

A matting agent can be used in the light-sensitive material and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952. In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40. Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. A specific example is U.S. Pat. No. 4,514,493.
And JP-A-62-65038.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye fixing element in order to enhance the storability of the light-sensitive material. In the present invention, EP 210,660, U.S. Pat.
Use is made of a combination of the hardly soluble metal compound described in No. 45 and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound). Specifically, JP-A-2-269,338 (2)-
It is described on page (6). Particularly preferred compounds as the sparingly soluble metal compound are zinc hydroxide, zinc oxide and a mixture of both.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development by interacting with a compound or silver and silver salt to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the back surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a stretcher, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, light sources described in U.S. Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources, can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivative nitroaniline derivatives, for example, 3-
Methyl-4-nitropyridine-N-oxide (POM)
The nitropyridine-N-oxide derivative as described above and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

The light-sensitive material and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
No. 45544 can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., but development at about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to promote dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably not lower than 50 ° C. and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C or higher and 100 ° C or lower. Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of formation accelerator are used)
Can be mentioned. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex forming compound may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material or both.
The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film). As a method for imparting a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (2)
6) There is a method described on page. Further, the solvent can be used by being incorporated in advance in the light-sensitive material or the dye-fixing element or both in the form of enclosing the solvent in microcapsules.

In order to promote dye transfer, a method of incorporating a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature into the light-sensitive material or the dye-fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye-fixing layer, but is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. And passing through a high temperature atmosphere. A pressure condition and a method for applying pressure when the light-sensitive element and the dye fixing element are superposed on each other and brought into close contact are disclosed in JP-A-61-1.
The method described in No. 47244, page 27 can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Shokai 62-259
No. 44, JP-A-3-131856 and JP-A-3-13185
The device described in No. 1 or the like is preferably used.

[0145]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 Synthesis of Exemplified Compound 3 In the synthesis of the dye of the present invention, a dye skeleton can be synthesized by a coupling reaction between a coupler moiety phenol and a 5-aminoisothiazole diazonium salt. Synthesis of 5-aminoisothiazoles is described in J. Heterocycl. Chem.,
12,883 (1975) or J.Org.Chem., 27,
The methods described in 2433 (1962) and references cited therein can be referred to. 1.0 g of 5-amino-3-methyl-4-cyanoisothiazole was dissolved in 25 ml of phosphoric acid, 0.65 g of sodium nitrite was added at 5 ° C. or lower, and the mixture was vigorously stirred for 30 minutes to prepare a diazonium solution. On the other hand, 1.11 g of 2-chlorophenol was dissolved in 30 ml of methanol, and the above diazonium solution was slowly added thereto at 10 ° C or lower with stirring. After stirring for 1 hour at 20 ° C. or less, 100 ml of ice water was added under stirring, the precipitated crystals were filtered, and the obtained crystals were recrystallized with 10 ml of methanol to obtain 0.85 g of dye 3. Melting point 220-222 ° C λmax
(DMF) 564.3nm

Example 2 Synthesis of Exemplified Compound 53 Exemplified compound 53 was synthesized by the following synthetic route.

[0147]

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(D) 200 ml of dimethylacetamide and 25 ml of 2-picoline were added to 71.8 g, and 25 g of 3-nitrobenzenesulfonyl chloride was added at 25 ° C. with stirring. After stirring at 25 ° C. for 2 hours, 1000 ml of cold water containing 10 ml of acetic acid was stirred and the precipitated crystals were filtered to obtain pale yellow crystals. The obtained crystals were recrystallized from 300 ml of acetonitrile to obtain pale yellow crystals (e). The obtained crystals were catalytically reduced with 300 ml of ethyl acetate and 3.5 g of 5% catalyst palladium / carbon. After filtering off the catalyst, ethyl acetate was concentrated to dryness, and methanol / water = 20/1 300 ml
Was crystallized and filtered to obtain 63.3 g of white crystals (f). Melting point 86-88 ° C (b) 2.53 g was dissolved in phosphoric acid 40 ml, sodium nitrite 1.6 g was added with stirring at -3 ° C, and the mixture was stirred at 0 ° C for 30 minutes. (A) 2.5 g was dissolved in 30 ml of methanol, and the diazonium solution was gradually added to the solution at 0 ° C. with stirring. After stirring at 20 ° C for another 30 minutes, cool water 150
The mixture was poured under stirring with ml, the precipitated crystals were filtered and further recrystallized with 15 ml of acetonitrile to obtain 4.4 g of yellow crystals (c). 30 ml of thionyl chloride was added to the obtained crystals, the mixture was refluxed for 1 hour, and then concentrated to dryness. On the other hand, 9.4 g of (f) was dissolved in 90 ml of dimethylacetamide, and the above acid chloride was gradually added to the mixture while cooling at 5 ° C. with stirring. After stirring for another 30 minutes, the mixture was poured into 300 ml of cold water and extracted with 200 ml of ethyl acetate. The ethyl acetate layer was washed twice with water and dried over magnesium sulfate. The magnesium sulfate was filtered off, concentrated to dryness, and crystallized with 80 ml of acetonitrile. The obtained crystals were filtered and then recrystallized from 70 ml of acetonitrile / ethyl acetate = 6/1 to obtain 7.4 g of red crystals (dye 53). Melting point 167-168
℃ λmax (DMF) 547.2nm

Example 3 The dyes shown in Table 1 were synthesized in the same manner as in Example 1 or 2. The dye number is the same as the dye number of the present invention. Table 1 shows λ max in DMF.

[0150]

[Table 1]

Example 4 A method for preparing a zinc hydroxide dispersion will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. The glass beads were separated to obtain a dispersion of zinc hydroxide.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

5 g of 10 g of the following electron transfer agent, 0.4 g of carboxymethyl cellulose (trade name: Serogen (6A) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant, and 0.2 g of the following anionic surfactant (A) were used. % Gelatin aqueous solution and milled for 60 minutes with glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0155]

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[0156]

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Next, a method for preparing a dye trapping agent dispersion will be described.

While stirring a mixed solution of 108 ml of the following polymer latex (A) (solid content 13%), 20 g of the following surfactant (1) and 1232 ml of water, 5 parts of the following anionic surfactant (B) was added. % Aqueous solution 600 ml was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Then 1
The same operation was repeated once again by adding 500 ml of water to obtain 500 g of the dye trapping agent dispersion.

[0159]

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[0160]

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[0161]

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Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Cyan, magenta and yellow dye-donor compounds and gelatin dispersions of electron donors are shown in Table 2, respectively.
I adjusted the prescription. That is, each oil phase component was heated and dissolved at about 60 ° C. to form a uniform solution. This solution and the aqueous phase component heated at about 60 ° C. were added, mixed with stirring, and dispersed with a homogenizer for 13 minutes at 12,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion. Further, regarding the gelatin dispersion of the magenta and cyan dye-donor compounds,
Ultrafiltration module (Asahi Kasei Ultrafiltration Module A
CV-3050) was used to repeat dilution with water and concentration, and the amounts of ethyl acetate and methyl ethyl ketone in Table 2 were reduced to 1/6.

[0164]

[Table 2]

[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For Red-sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and the following chemicals) (A) Add 15mg and 42 ℃
Solution (I) and solution (II) in Table 2 were simultaneously added at a constant flow rate for 8 minutes. Then, 8 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of a dye (water 1) was added.
1.9 g of gelatin in 60 ml, the following pigment (a) 127
mg, the following pigment (b) 253 mg, the following pigment (c) 8 mg
Containing 35 ° C. and kept at 35 ° C.). After 2 minutes, the liquids (III) and (IV) in Table 3 were further added simultaneously at the same flow rate for 32 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1), chemical (C ) 80 mg and 3 g of the chemical (D) were added and then cooled. Thus, the average particle size is 0.21 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0182]

[Table 3]

[0183]

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[0184]

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[0185]

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[0186]

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Photosensitive Silver Halide Emulsion (2) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 ml of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 700 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 53 ° C.), the liquids (I) and (II) in Table 4 were simultaneously added at an equal flow rate for 10 minutes. Then, 6 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of the dye (115 ml of water) was added.
Including 1.2 g of gelatin, 77 mg of the above dye (a), 153 mg of the above dye (b), and 5 mg of the above dye (c).
(Preserved at 5 ° C.). After 4 minutes, solution (III) and solution (IV) shown in Table 4 were further added simultaneously at the same flow rate for 30 minutes.

After washing with water and desalting in the usual way, 33 g of lime-treated ossein gelatin and 50 mg of the above-mentioned chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6-. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added to optimally perform chemical sensitization at 68 ° C., and then the antifoggant (1), chemical (C ) 80 mg and 3 g of the chemical (D) were added and then cooled. Thus, the average particle size is 0.45 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0189]

[Table 4]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 41 ° C.), the liquids (I) and (II) in Table 5 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 5 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after the addition of the liquids I) and (IV) was completed, 280 mg of the following dye (d) in a methanol solution of the dye (47 ml of methanol) was added.
Which was kept at 30 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.1. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 60 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.23 μm was prepared.
5 g were obtained.

[0192]

[Table 5]

[0193]

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Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 690 ml of water).
g and the above-mentioned chemical (A) 7.5 mg were added and kept at 63 ° C.), and the liquids (I) and (II) in Table 6 were simultaneously added to 10 parts.
Add at an equal flow rate for minutes. After 10 minutes, solution (III) and solution (IV) in Table 6 were further added simultaneously at an equal flow rate for 20 minutes. Also (I
One minute after the completion of the addition of the solutions (II) and (IV), a methanol solution of the dye (a solution containing 170 mg of the dye (d) in 35 ml of ethanol and kept at 46 ° C.) was added all at once.

After washing with water and desalting in the usual way, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.2. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 60 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0196]

[Table 6]

Photosensitive Silver Halide Emulsion (5) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 5 in 690 ml of water).
g and the above-mentioned chemical (A) (15 mg) and the mixture was kept at 46 ° C.), solution (I) and solution (II) in Table 7 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) in Table 7 were simultaneously added at the same flow rate for 18 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 9
225 mg of the following dye (e) in 5 ml and 5 ml of methanol
And the following dye (f) containing 225 mg and kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Addition of tetrazaindene, then sodium thiosulfate, optimal chemical sensitization at 65 ° C, then addition of the following antifoggant (1) followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.27 μm was prepared.
5 g were obtained.

[0199]

[Table 7]

[0200]

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[0201]

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Photosensitive Silver Halide Emulsion (6) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 59 ° C.), the solutions (I) and (II) in Table 8 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 8 were added simultaneously at an equal flow rate for 18 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 8
113 mg of the above dye (e) in 2 ml and 6 ml of methanol
And the above-mentioned dye (f) containing 113 mg and kept at 40 ° C.) were added all at once.

After washing with water and desalting in the usual way, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 65 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.

[0204]

[Table 8]

Photosensitive materials K101 shown in Tables 9 to 11 were prepared using the above materials.

[0206]

[Table 9]

[0207]

[Table 10]

[0208]

[Table 11]

[0209]

Embedded image

[0210]

Embedded image

[0211]

Embedded image

[0212]

Embedded image

[0213]

Embedded image

Next, a light-sensitive material K1 was prepared except that a dye-donor compound corresponding to the general formula (2) was used as a dye-donor compound.
In the same manner as in 01, the photosensitive material K as shown in Table 12
102-K105 were created.

[0215]

[Table 12]

Next, a method for preparing the dye fixing material will be described. Dye fixing material R having a constitution as shown in Tables 13 and 14
Made 101.

[0219]

[Table 13]

[0218]

[Table 14]

[0219]

Embedded image

[0220]

Embedded image

[0221]

Embedded image

[0222]

Embedded image

[0223]

Embedded image

Using the above photosensitive materials K101 to 105 and the dye fixing material R101, a standard color image was taken using a Pictrostat 300 manufactured by Fuji Photo Film Co., Ltd. A clear color image was obtained using a processed positive of Fuji Color Velvia. It was The image obtained for the evaluation of the fastness to light was covered with an ultraviolet cut filter, and left in a xenon fading tester for 14 days. The change in magenta density of the color image density before and after standing under the above conditions was evaluated using a reflection densitometer (X-Rite 310TR manufactured by X-Rite). The experimental results are shown in Table 15.

[0225]

[Table 15]

As compared with the dye images obtained with the dye-donor compound of Comparative Example, the dye image using the dye-donor compound of the present invention showed significantly less fading by light.

Example 5 A method for preparing a gelatin dispersion of a dye-donor compound will be described. 4.50 magenta dye-donor compound (B)
g, compound (m) 0.05 g, compound (h) 0.0
5 g, 0.094 g of the surfactant (5) and 2.25 g of the high boiling point solvent (7) were weighed, 10 ml of ethyl acetate was added,
The mixture was dissolved by heating at about 60 ° C. to form a uniform solution. This solution, 15.2 g of a 16% solution of lime-processed gelatin and 23.5 g of water
After mixing cc with stirring, 10 minutes with a homogenizer, 10
Dispersed at 000 rpm. After that, 42 cc of dilution water was added. This dispersion is referred to as a dispersion of a magenta dye-donating compound.

[0228]

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Next, a method for preparing a gelatin dispersion of the compound (d) will be described. 0.4 g of compound (d), 1.2 g of high boiling solvent (6), 0.12 g of compound (f), 0.25 g of compound (g), 0.05 g of compound (h), surfactant 0.2 g of (5) was weighed, and ethyl acetate was added to 9.5
cc was added and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 29.1 g of an 18% lime-processed gelatin solution were mixed by stirring, and then a homogenizer was used for 10 minutes at 10,000 rp.
m. After the dispersion, 18.5 cc of water for dilution was added. This dispersion is referred to as a dispersion of the compound (d).

[0230]

Embedded image

By these, a light-sensitive material K201 as shown in Tables 16 to 17 was constructed.

[0232]

[Table 16]

[0233]

[Table 17]

[0234]

Embedded image

[0235]

Embedded image

Photosensitive materials K202 to K205 as shown in Table 18 were prepared in the same manner as the photosensitive material K201 except that the magenta dye-donating compound corresponding to the general formula (2) was used. . Further, the mordant (1) of the third layer and the second layer of the dye fixing material R101 was replaced with the polymer latex A, and the coating amount was 150 respectively.
Dye fixing material R except that the amount is mg / m ² , 1500 mg / m ²
A dye fixing material R102 was prepared in exactly the same manner as 101.

[0237]

[Table 18]

Fuji Color Super G400AC in which an image of a stepwise wedge pattern was photographed by using the above-mentioned photosensitive materials K201 to K205 and the dye fixing material R102 and using Pictrostat 330 manufactured by Fuji Photo Film Co., Ltd.
A stepwise magenta image was obtained using the processed negative of E.
In addition to the same experiment as in Example 4, the image was left in an atmosphere of 80 ° C.-70% RH for 7 days in order to evaluate the fastness to heat and humidity. As in Example 4, the change in magenta density before and after standing was evaluated. The experimental results are shown in Table 19.

[0239]

[Table 19]

As compared with the dye images obtained with the dye-donor compounds of Comparative Examples, the dye images using the dye-donor compound of the present invention showed significantly less fading due to light, humidity and temperature.

Example 6 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Photosensitive Layer)] Aqueous solutions having the compositions shown in Table 20 and (I) and (II) having the compositions shown in Table 21 were stirred well. ) Solution was added simultaneously over 13 minutes, and 10 minutes later, (II) having the composition shown in Table 21 was added.
Solution I and solution IV were added over 33 minutes.

[0243]

[Table 20]

[0244]

[Table 21]

[0245]

Embedded image

Further, 13 minutes after the addition of the solution III is started and 27 minutes thereafter, an aqueous solution containing 0.350% of the sensitizing dye is added.
0 cc was added.

After washing with water and desalting according to a conventional method (the precipitation agent a was used at a pH of 4.1), 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.9. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 22. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0248]

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[0249]

[Table 22]

[0250]

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[0251]

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Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Sensitive Layer)] Aqueous solutions having the compositions shown in Table 23 and (II) and (II) having the compositions shown in Table 24 were stirred well. Solution) was added simultaneously for 18 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 24 were added over 24 minutes.

[0253]

[Table 23]

[0254]

[Table 24]

After washing with water and desalting (pH was set to 3.9 using the precipitating agent b) by a conventional method, calcified lime-treated ossein gelatin (calcium content: 150 PPM) was used.
22 g) and redispersed at 40 ° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added, pH is 5.9 and pAg is 7. 8
Adjusted to. Then, use the chemicals shown in Table 25 at 70 ° C.
With chemical sensitization. At the end of the chemical sensitization, the sensitizing dye was added as a methanol solution (solution having the composition shown in Table 26). Further, after the chemical sensitization, the temperature was lowered to 40 ° C., and 200 g of a gelatin dispersion of a stabilizer described later was added. The yield of the obtained emulsion was 938 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0256]

[Table 25]

[0257]

[Table 26]

[0258]

Embedded image

Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] Aqueous solutions having the compositions shown in Table 27 and (I) and (II) having the compositions shown in Table 28 were stirred well. Solution) was added simultaneously for 18 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 28 were added over 24 minutes.

[0260]

[Table 27]

[0261]

[Table 28]

After washing with water and desalting (the precipitation agent a was used at a pH of 3.8) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.4 and pAg to 7.8. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 29. The yield of the obtained emulsion was 680 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0263]

[Table 29]

A method for preparing fine grain silver chloride to be added to the first layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 30, the solutions A and B having the composition shown in Table 31 were simultaneously added over 4 minutes, and after 5 minutes, the solution C having the composition shown in Table 31 was added. Solution D was added over 8 minutes. 2 minutes after the end of addition, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.7 g was added. After washing with water and desalting (the precipitation agent a was used at pH 3.9) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 5.7 and pAg to 6.8. The resulting emulsion had an average grain size of 0.
The yield was 530 g with 08 μm of monodispersed silver chloride.

[0266]

[Table 30]

[0267]

[Table 31]

A method for preparing a gelatin dispersion of colloidal silver will be described.

The liquid having the composition shown in Table 33 was added to the aqueous solution having the composition shown in Table 32, which was well stirred, for 24 minutes. After that, the precipitate was washed with water using a precipitating agent a, and then 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02μm and the yield is 512g.
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0270]

[Table 32]

[0271]

[Table 33]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Gelatin dispersions of a yellow dye-donor compound, a magenta dye-donor compound and a cyan dye-donor compound were prepared according to the formulations shown in Table 34. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution. The aqueous phase component heated to about 60 ° C. was added to this solution, followed by stirring and mixing, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.
In addition, a gelatin dispersion of a cyan dye-donating compound was added to an ultra-loca module (Asahi Kasei ultra-loca module: ACV).
-3050) was repeatedly diluted with water and concentrated, and the amount of ethyl acetate was reduced to 17.6 times the amount of ethyl acetate in Table 34.

[0274]

[Table 34]

A gelatin dispersion of the antifoggant is shown in Table 3.
Prepared according to Formulation No. 5. That is, the oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes to 100
The dispersion was performed at 00 rpm to obtain a uniform dispersion.

[0276]

[Table 35]

A gelatin dispersion of reducing agent was prepared according to the recipe in Table 36. That is, the oil phase component is heated and dissolved at about 60 ° C., and the aqueous phase component heated to about 60 ° C. is added to this solution,
After stirring and mixing, use a homogenizer for 10 minutes, 10,000
Dispersed at rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[0278]

[Table 36]

A dispersion of polymer latex (a)
Prepared according to prescription in Table 37. That is, the anionic surfactant was added over 10 minutes while stirring a mixed solution of the polymer latex (a), the surfactant and water in the amounts shown in Table 37 to obtain a uniform dispersion. Further, the obtained dispersion is used as an ultra loca module (ultra loca module made by Asahi Kasei: ACV
-3050) was repeatedly diluted with water and concentrated to prepare a dispersion having a salt concentration of 1/9.

[0280]

[Table 37]

A gelatin dispersion of the stabilizer was prepared as per the formulation in Table 38. That is, the oil phase component is dissolved at room temperature,
The aqueous phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed, and then homogenized for 10 minutes at 10,000 rpm.
Was dispersed. Water was added thereto and stirred to obtain a uniform dispersion.

[0282]

[Table 38]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 39. That is, after mixing and dissolving each component, a glass mill with an average particle size of 0.75 mm
Dispersed for minutes. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.1.
The thing of 25 micrometers was used. )

[0284]

[Table 39]

Next, a method for preparing a gelatin dispersion of the matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolventizer to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0286]

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[0287]

Embedded image

[0288]

Embedded image

[0289]

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[0290]

Embedded image

[0291]

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[0292]

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[0293]

Embedded image

[0294]

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[0295]

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[0296]

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[0297]

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[0298]

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[0299]

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Photothermographic materials K301 shown in Tables 40 and 41 were produced using the above materials.

[0301]

[Table 40]

[0302]

[Table 41]

Photosensitive materials K302 to K302 shown in Table 42 were prepared in exactly the same manner except that the dye-donor compound corresponding to the general formula (2) was used as the magenta dye-donor compound.
K305 was created.

[0304]

[Table 42]

Using the above photosensitive materials K301 to K305 and the dye fixing material R102, Fuji Photo Film Co., Ltd. Digital Full Color Printer Pictrography PG3
000 was used to obtain a stepped magenta image. Example 5
When the same experiment was conducted, the result showed the same tendency as in Example 5. The experimental results are shown in Table 43.

[0306]

[Table 43]

As compared with the dye images obtained with the dye-donor compounds of Comparative Examples, the dye images using the dye-donor compound of the present invention showed significantly less fading due to light, humidity and temperature.
The same tendency was observed when the dye fixing element R101 was used, and the photobleaching was small.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 30, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

The general formula (1) will be described in detail below. In R ¹ , R ² , R ³ , and R ⁴ , a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, an alkoxy group, An aryloxy group,
Heterocyclic oxy group, silyloxy group, alkylthio group,
Arylthio group, heterocyclic thio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonamide group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, carbamoylamino group,
A carbamoyloxy group, a sulfamoylamino group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an aryloxycarbonyloxy group, and a sulfonyloxy group are preferable from the viewpoint of the effect of the present invention. More specifically, R ¹ , R ² ,
R ³ and R ⁴ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a carbon number of 12 or less, preferably a carbon number). 8 or less optionally substituted alkyl groups, for example, methyl group, trifluoromethyl group, benzyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, n -Propyl group,
iso-propyl group, n-butyl group, t-butyl group, t
-Pentyl group, cyclopentyl group, n-hexyl group, t
-Hexyl group, cyclohexyl group, n-octyl group, n
-Decyl group, n-undecyl group, n-dodecyl group, etc.), aryl group (C18 or less, preferably C10 or less aryl group which may be substituted. For example, phenyl group, naphthyl group, 3- Hydroxyphenyl group, 3-
Chlorophenyl group, 4-acetylaminophenyl group, 2
-Methanesulfonylphenyl group, 4-methoxyphenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc., heterocyclic group (having 18 or less carbon atoms,
A heterocyclic residue having preferably 10 or less carbon atoms which may be substituted. For example, 1-imidazolyl group, 2-furyl group, 2
-Pyridyl group, 3-pyridyl group, 3,5-dicyano-2
-Pyridyl group, 5-tetrazolyl group, 5-phenyl-1
-Tetrazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazolin-2-yl group, morpholino group, etc., acyl group (C12 or less, preferably C8 or less) Optionally substituted acyl groups such as acetyl group, propionyl group, butyroyl group, iso-butyroyl group, 2,2-
Dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3-acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, etc., sulfonyl group (having 12 or less carbon atoms, preferably 8 or less carbon atoms) Optionally a sulfonyl group, for example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-
Octanesulfonyl group, n-dodecanesulfonyl group, benzenesulfonyl group, 4-methylphenylsulfonyl group, etc.),

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

R ⁵ is a hydrogen atom, an alkyl group (having 12 carbon atoms
Hereafter, an alkyl group which preferably has 8 or less carbon atoms and may be substituted, for example, a methyl group, a trifluoromethyl group, an acetylaminomethyl group, an ethyl group, a carboxyethyl group, an allyl group, an n-propyl group, and iso-propyl Group,
n-butyl group, t-butyl group, t-pentyl group, cyclopentyl group, n-hexyl group, t-hexyl group, cyclohexyl group, t-octyl group, n-decyl group, etc.),
Preferably, an aryl group such as a chlorine atom or a bromine atom (an optionally substituted aryl group having 18 or less carbon atoms, preferably 10 or less carbon atoms, for example, a phenyl group, a naphthyl group, 3
-Hydroxyphenyl group, 3-chlorophenyl group, 4-
Acetylaminophenyl group, 2-methanesulfonylphenyl group, 4-methoxyphenyl group, 2,4-dimethylphenyl group, etc., heterocyclic group (having 18 or less carbon atoms, preferably 10 or less carbon atoms may be substituted). A heterocyclic group,
For example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 2-thienyl group, etc., alkoxy group (C 12 or less, preferably 8 or less, optionally substituted alkoxy group such as methoxy group) , Ethoxy group, i-propyloxy group, methoxyethoxy group, etc., cyano group, alkylthio group (C12 or less, preferably C8 or less alkylthio group, for example, methylthio group, ethylthio group, n-butylthio group, Benzylthio group) and an alkylsulfonyl group (C12 or less, preferably C8 or less, alkylsulfonyl group such as methanesulfonyl group, butanesulfonyl group, etc.). Preferred among these are a hydrogen atom and an alkyl group.

Claims (2)

[Claims] 1. 4- (5-) represented by the following general formula (1):
Isothiazolylazo) phenol dye. Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. R ³ and R ⁴ may combine with each other to form a ring structure. R ⁵ is a hydrogen atom, a halogen atom,
Alkyl group, aryl group, heterocyclic group, alkoxy group,
It represents a cyano group, an alkylthio group, or an alkylsulfonyl group. R ⁶ represents a cyano group, a nitro group, a thiocyano group, an alkoxycarbonyl group or a carbamoyl group. 2. A color photographic light-sensitive material comprising at least one dye-donor compound represented by the following general formula (2) on a support. General formula (2) (Dye-X) q-Y In the formula, Dye is the 4- (5-isothiazolylazo) phenol dye represented by the general formula (1) according to claim 1 or its precursor. Represents a dye moiety having three or more, X represents a mere bond or linking group which is cleaved in response to or corresponding to development, and Y corresponds to or inversely corresponds to reaction of a photosensitive silver salt having a latent image on an image. Represents a group having a property of causing a difference in diffusibility of the dye portion. Dye and X are R ¹ , R ² , R ³ of the general formula (1) according to claim 1,
It bonds at at least one of R ⁴ and R ⁵ . q is 1
Or 2, and when q is 2, Dye-X may be the same or different.