JPH07301898A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material small in susceptibility to fluctuation of development processing conditions and improved in storage stability and superior in discrimination performance by using a novel diffusive magenta dye-forming coupler obtained by combining a diffusive magenta dye group with a diffusive magenta dye donative group through a divalent bonding group substituted by a cyclic amino group. CONSTITUTION:The photosensitive material contains the magenta dye donor represented by the formula in which Dye is the magenta dye group or its precursing group on a supporting body; A is a group to be cleft at the A-L bond; L is the divalent bonding group substituted by the cyclic amino group; and each of monomer is an integer of >=1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a diffusion transfer type silver halide photographic light-sensitive material, and more particularly to a diffusible magenta dye-donor compound for use in the light-sensitive material.

[0002]

2. Description of the Related Art Techniques for forming an image with a diffusion transfer type silver halide photographic light-sensitive material can be classified into two methods. One is a method of designing so that the diffusivity of the dye molecule itself changes in response to the development reaction of the exposed silver halide, and the other is a method in the light-sensitive material as a dye-donor compound immobilized by a ballast group. It is a method designed to release the diffusible dye from the dye-donor compound in response to or against the development reaction of silver halide.

As a method for releasing the diffusible dye from the dye-donor compound, a method using a coupling reaction between an oxidized product of a developing agent and a dye-releasing coupler having the diffusible dye as a leaving group, or a redox reaction is used. Of using a diffusible dye-releasing redox compound having the property of cleaving the bond between the diffusible dye moiety and the redox mother nucleus moiety immobilized by a ballast group by a subsequent reaction, and interaction with silver ion Compounds that release diffusible dyes are known. Further, these diffusible dye-providing compounds are classified into a negative-working compound that releases a diffusible dye corresponding to the development of silver halide and a positive-acting compound that releases the diffusible dye correspondingly to the development depending on the development reaction of silver. Can be classified.

In diffusible dye-releasing redox compounds, examples of negative-working compounds are shown in US Pat. No. 3,928,312.
No. 4,135,929, 4,053,312
Nos. 4,336,322 and 4,055,428, and sulfonamide phenols disclosed in JP-A-51
-104,343, JP-A-53-46,730, compounds disclosed in JP-A-53-3,819, JP-A-62-18,908 and 61-48,8
No. 48, Research and Disclosure (1975), page 22, and US Pat.
The hydrazides disclosed in Nos. 844,785 and 4,684,604 are known.

As examples of positive-working compounds, the BEND compounds disclosed in US Pat. Nos. 4,139,379 and 4,139,389 and the Carquin compounds disclosed in British Patent 11,445 are well known. There is. Further, the positive-acting redox compound utilizing the nitrogen-oxygen bond cleavage reaction by one-electron reduction disclosed in JP-A-62-215270 is excellent in storage stability, alkali resistance and reduction-dye releasing efficiency. It is a compound.

Now, in the study of a diffusion transfer type silver halide photographic light-sensitive material using a diffusible dye-donating compound,
To obtain a more excellent image of discrimination,
Another problem is to provide a light-sensitive material having less temperature dependency during processing. Here, examples of the negative-acting compound of the diffusible dye-donating compound include JP-A Nos. 58-149046, 59-154445 and 5
9-165054, 59-180548, U.S. Pat. Nos. 4,503,137, 4474867, and 4
Consider, for example, the heat-development image forming system described in US Pat. No. 4,83,914 and US Pat. No. 4,455,363.
In this system, the diffusible dye-donor compound itself acts as a reducing agent for silver halide, releasing a mobile dye. Therefore, in the dye-donating compound, not only the structure of the reducing group has a great influence on the silver developability, but also the structure of the dye group or the linking group connecting the dye group and the reducing group is a factor that influences the silver developability. This makes it difficult to design a diffusible dye-donating compound that achieves both discrimination and processing temperature dependence.

Examples of the linking group connecting the dye group and the reducing group include those disclosed in the diffusible dye-providing compound described in US Pat. No. 3,954,476. Among these, there is a description about a dye-donating compound having an amino group as a linking group, but there is no description about a specific compound, and there is no description about an effect obtained by substituting an amino group.

Further, when a diffusible dye-donating compound having a linking group substituted with a dimethylamino group is used in the system for obtaining an image by thermal development as described in JP-A-58-149046, the discrimination is Is getting worse,
Further, it was found that the processing temperature dependency was relatively large. Further, it has been found that when these compounds are used, discrimination is deteriorated when left for a long period of time or under severe conditions (high temperature and / or high humidity) before exposure or development processing.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a light-sensitive material which is excellent in discrimination and has small processing temperature dependence.

[0010]

Means for Solving the Problems As a result of intensive studies by the present inventors, an image excellent in discrimination was obtained by using a diffusible magenta dye-donating compound represented by the following general formula (1). In addition, it has become possible to provide a photographic material which is compatible with the improvement of processing temperature dependency and has excellent storage stability. The above is surprising, which cannot be expected from conventional knowledge. General formula (1)

[0011]

[Chemical 2]

In the formula, A represents a group having the property of immobilizing the magenta dye-donating compound of the general formula (1) in the light-sensitive material and cleaving the AL bond in the processing reaction after exposure. Dye represents a magenta dye group or a magenta dye precursor group. L represents a divalent linking group substituted with a cyclic amino group. m and n represent an integer of 1 or more.

Next, the compound of the general formula (1) will be described. First, A will be described. A represents a group having a property of cleaving the A-L bond corresponding to or inversely corresponding to the 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 US Pat. No. 5,021,334 (Japanese Patent Laid-Open No. 18485/1990).
No. 2).

A will be described in detail. (1) As A, first, a negative-working group that releases a diffusible dye corresponding to development can be mentioned.

As A classified as a negative-working group, a group which releases a diffusible dye from an oxidant is known. The following formula (A-1) is mentioned as a preferable example of this type A. (A-1)

[0016]

[Chemical 3]

In the formula, β represents a group of non-metal atoms necessary for forming a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle. α is −
Represents OZ ² or —NHZ ³ , wherein Z ² represents a hydrogen atom or a group capable of generating a hydroxyl group by hydrolysis, Z ^2
3 represents a hydrogen atom, an alkyl group, an aryl group, or a group capable of generating an amino group by hydrolysis. Z ¹ is an optionally substituted alkyl group, aryl group, aralkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, sulfonyl group, acylamino group, sulfonylamino group, carbamoyl group, It represents a sulfamoyl group, a ureido group, a urethane group, a heterocyclic group or a cyano group, a halogen atom, a represents a positive integer, and when Z ¹ is 2 or more, they may be the same or different. * Represents a position to be bonded to L.

Among the groups contained in (A-1), preferable groups include (A-2) and (A-3). (A
-2)

[0019]

[Chemical 4]

(A-3)

[0021]

[Chemical 5]

In the formula, Z ² and * have the same meanings as described in (A-1). Z ⁵ and Z ⁶ represent an alkyl group, an aryl group or an aralkyl group, and these may have a substituent. Furthermore Z
⁵ is a secondary or tertiary alkyl group, Z ⁵ and Z ⁶
It is preferable that the sum of the number of carbon atoms is 20 or more and 50 or less.

Specific examples of these are described 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, No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, and No. 57-40.
No. 43, No. 59-60, 439, Japanese Patent Publication No. 56-176
56 and 60-25780.

Another example of the negative acting group is (A-
4) is mentioned. (A-4)

[0025]

[Chemical 6]

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

Of the groups represented by (A-4), α is -OZ
^{It is 2} that β ′ forms a naphthalene skeleton. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

Further, as negative-working groups which release diffusible dyes by the same reaction as (A-1) and (A-4), JP-A Nos. 51-104343, 53-46730 and 54
-130122, 57-85055, 53-3
No. 819, No. 54-48534, No. 49-64436.
No. 57-20735, JP-B-48-32129
No. 48-39165, U.S. Pat. No. 3,443,93.
The groups described in No. 4 are mentioned.

Examples of the negative acting group which releases the diffusible dye from the oxidant by another reaction mechanism include the hydroquinone derivative represented by the formula (A-5) or (A-6). (A-5)

[0030]

[Chemical 7]

(A-6)

[0032]

[Chemical 8]

In the formula, β'and * are the same as those in formula (A-4), Z ² is the same as that in formula (A-1), Z ⁷ is the same as Z ² , and Z ⁸ is the same as Z ¹ . Represents a substituent or a hydrogen atom. Z ² and Z ⁷ may be the same or different.
Specific examples of this type are described in US Pat. No. 3,725,062.

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 A is US Pat.
P-hydroxydiphenylamine derivatives described in U.S. Pat. No. 3,939, U.S. Pat. No. 3,844,785, U.S. Pat. D. The hydrazine derivative described in No. 128, page 22 may be mentioned.

Still another negative acting group is represented by the following formula (A
-7) can be mentioned. (A-7)

[0037]

[Chemical 9]

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. Specific examples are described in British Patent 1,330,524. * Represents a position to be bonded to L.

(2) Next, as A, there can be mentioned a positive working group which releases a photographically useful group in the opposite manner to development.

Examples of the positive-working group include a group that exhibits a function when reduced during treatment. This type of A
The following formula (A-8) is a preferred example of
(A-8)

[0041]

[Chemical 10]

In the formula, * represents the position at which L is bonded. EA
G 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 -
The N-W bond is cleaved after EAG receives an electron. Z ¹¹ represents an alkyl group or an aryl group. Z ⁹ ,
Z ¹⁰ represents a mere bond or a substituent other than a hydrogen atom. A solid line represents a bond, and a broken line represents that at least one of them is bonded to L.

Preferred among the groups represented by (A-8) are formula (A-9). (A-9)

[0044]

[Chemical 11]

In the formula, EAG, *, have the same meanings as (A-8), O represents an oxygen atom (that is, W in (A-8) is an oxygen atom), and Z ¹² represents an N—O bond. the heterocyclic ring formed include, and subsequent to cleavage of the N-O bond represents an atomic group having a property of Z ¹² -G bond is cleaved. Z ¹² may have a substituent and a saturated or unsaturated ring may be condensed. Z ¹³ represents -CO- or -SO ₂ - represents a.

More preferred groups of (A-9) include (A-10). (A-10)

[0047]

[Chemical 12]

In the formula, * represents a position to be bonded to L, and Z represents
¹⁴ represents an alkyl group, an aryl group or an aralkyl group, and 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, an aryloxy group, an arylthio group, a halogen atom, a cyano group or a nitro group, and b is 0.
Represents an integer of 3 to 3. The substitution position of the nitro group in the formula is ortho or para to the nitrogen atom. Furthermore Z ¹⁵
Most preferably, is a carbamoyl group or sulfamoyl group substituted with an alkyl group having 12 to 30 carbon atoms.

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

Other positive-working groups capable of exhibiting functions upon reduction include US Pat. Nos. 4,139,379 and 4,4.
BEND compounds described in 139,389,
Carquin compounds described in British Patent No. 11,445, JP-A-54-126535 and JP-A-57-844.
The groups described in No. 53 can be mentioned.

When these reducible groups represented by A represented by (A-8) are used, a reducing agent is used in combination, but an LDA compound containing a reducing group in the same molecule. Can also be mentioned. This is described in US Pat. No. 4,551,423.

There is also a type of positive-working group which is incorporated in the light-sensitive material as a reductant and deactivates when oxidized during processing. Japanese Patent Application Laid-Open No. 51-6
F described in 3618 and US Pat. No. 3,980,479
ields compound and JP-A-49-111628 and 52-
H described in 4819 and US Pat. No. 4,199,354
inshaw compounds.

Examples of this type A include (A-11). (A-11)

[0054]

[Chemical 13]

In the formula, * represents the position at which L is bonded,
Z ¹⁷ and Z ¹⁹ represent a hydrogen atom or a substituted or unsubstituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and Z ¹⁸ represents an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, carbamoyl group, sulfonyl group,
It represents a sulfamoyl group, and Z ²⁰ and Z ²¹ represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. Specifically, JP-A-62-245,270
No. 63-46450.

As a positive-working group having another mechanism, a thiazolidine type group can be mentioned. Specifically, US Pat.
68,451.

Of these A's, a negative acting group is more preferred. More preferred are the negative acting groups described in JP-A-58-149046.

Next, Dye will be described. Dye used in the present invention is a magenta dye. Examples of magenta dyes include azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, and triarylmethane dyes. In addition, those leuco compounds, those whose absorption wavelength is temporarily shifted, and dye precursors such as tetrazolium salts are also included. Further, these dyes may form chelate dyes with suitable metals. Among these, azo dyes are particularly preferable.

Examples of magenta dyes: US Pat. No. 3,453,3
No. 107, No. 3,544,545, No. 3,932,3
80, 3,931,144, 3,932,30
No.8, No.3,954,476, No.4,233,237
Nos. 4,255,509 and 4,250,246
No. 4,142,891, No. 4,207,104
No. 4,287,292: JP-A-52-10672
No. 7, No. 53-23628, No. 55-36804,
56-73057, 56-71060, 55.
-134.

As a kind of dye precursor portion, specific examples of the dye whose light absorption is temporarily shifted in the light-sensitive element are shown in US Pat. Nos. 4,310,612 and 3,57.
9, 334, and JP-A-57-158638.

Next, L will be described. L represents a divalent linking group substituted with a cyclic amino group, and is represented by the following formula (L-1). (L-1)

[0062]

[Chemical 14]

In the formula, ** represents the position of bonding to A, *** represents the position of bonding to Dye, and γ represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle. The ring may be condensed with a saturated or unsaturated carbocycle or heterocycle. Moreover, these may have a substituent. Preferred examples of the cyclic amino group include a heterocyclic ring (which may have a substituent) having 4 to 6 ring members (eg, pyrrolidine, 2
-Carboxypyrrolidine, pyrazolidine, indoline,
Piperidine, N-methylpiperazine, morpholine, etc.)
Are preferred, but pyrrolidine and morpholine are more preferred.

Examples of the group preferably used as X include a benzene ring and a naphthalene ring, which may have a substituent.

Another preferred group is a heterocyclic ring containing 1 or 2 nitrogen atoms, which may have a substituent, or may be condensed with another ring (eg pyrrole). , Pyrazole, imidazole, pyrroline, pyrazoline, imidazoline, pyrrolidine, pyrazolidine, imidazolidine, indole, indoline, pyridine, pyrimidine, pyrazine, piperidine, pyridoneadenine, tetrahydropyrimidine, morpholine, quinoline, quinoxaline, N-methylmorpholine, oxindole, Hydantoin and the like).

Another preferred group is a chain or cyclic alkyl group having 2 to 10 carbon atoms (for example,
Ethane, propane, butane, pentane, hexane, isobutane, cyclopentane, cyclohexane, cycloheptane, decane, cyclodecane, etc., and a group partially containing an oxygen atom or a sulfur atom (eg, furan, tetrahydrofuran, pyran). , Tetrahydropyran, di-n-butyl ether, thiophene, tetrahydrothiophene) can also be used.

Among these, more preferable groups include a benzene ring, a naphthalene ring, and a chain or cyclic alkyl group having 2 to 6 carbon atoms. Further, from the viewpoint of ease of synthesis and versatility, a benzene ring is preferable. Are most preferred.

When X has a substituent, preferable groups are an alkyl group and an aralkyl group (an alkyl group and an aralkyl group which may be substituted. For example, a methyl group, a trifluoromethyl group, a benzyl group, a chloromethyl group and dimethyl group. Aminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, 3,3,3-trichloropropyl group, n-propyl group, iso-propyl group, n- Butyl group, iso-butyl group, sec-butyl group, t-butyl group,
n-benzyl group, sec-pentyl group, t-pentyl group,
Cyclopentyl group, n-hexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, sec-octyl group, t-octyl group, n-decyl group, n-undecyl group, n-dodecyl group , N-tetradecyl group, n-pentadecyl group, n-hexadecyl group, s
ec-hexadecyl group, t-hexadecyl group, n-octadecyl group, t-octadecyl group, etc.),

Alkenyl group (Alkenyl group which may be substituted. For example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexene-
1-yl group, etc.), alkynyl group (optionally substituted alkynyl group, for example, ethynyl group, 1-propynyl group, 2-ethoxycarbonylethynyl group, etc.),

Aryl group (aryl group which may be substituted. For example, phenyl group, naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group. , 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc.),

Acyl group (acyl group which may be substituted. For example, acetyl group, propionyl group, butyroyl group, i
so-butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3
-Acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, 4-methoxy-3-sulfobenzoyl group, etc.),

Sulfonyl group (a sulfonyl group which may be substituted. For example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, 4-
Toluenesulfonyl group, etc.),

A carbamoyl group (a carbamoyl group which may be substituted, for example, a carbamoyl group, a methylcarbamoyl group, a dimethylcarbamoyl group, a bis- (2-methoxyethyl) carbamoyl group, a diethylcarbamoyl group, a cyclohexylcarbamoyl group),

Sulfamoyl group (sulfamoyl group which may be substituted. For example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, bis- (2-methoxyethyl) sulfamoyl group, di- n-butylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, etc.),

An alkoxy or aryloxycarbonyl group (optionally substituted alkoxy or aryloxycarbonyl group, for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, 2-methoxyethoxycarbonyl group, etc.),

Alkoxy or aryloxysulfonyl group (alkoxy or aryloxysulfonyl group which may be substituted. For example, methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, 2-methoxyethoxysulfonyl group, etc.),

Alkoxy or aryloxy group (alkoxy or aryloxy group which may be substituted.
For example, methoxy group, ethoxy group, methoxyethoxy group,
2-chloroethoxy group, phenoxy group, p-methoxyphenoxy group, etc.),

Alkylthio or arylthio group (optionally substituted alkylthio or arylthio group.
For example, methylthio, ethylthio, n-butylthio, phenylthio, 4-chlorophenylthio, 2-methoxyphenylthio, etc.),

Amino group (optionally substituted amino group, for example, amino group, methylamino group, N, N-dimethoxyethoxyamino group, methylphenylamino group, etc.),

An ammonio group (an ammonio group which may be substituted, for example, an ammonio group, a trimethylammonio group, a phenyldimethylammonio group, a dimethylbenzylammonio group, etc.),

Acylamino group (acylamino group which may be substituted. For example, acetylamino group, 2-carboxybenzoylamino group, 3-nitrobenzoylamino group,
3-diethylaminopropanoylamino group, acryloylamino group, etc.),

Acyloxy group (acyloxy group which may be substituted, for example, acetoxy group, benzoyloxy group, 2-butenoyloxy group, 2-methylpropanoyloxy group, etc.),

Sulfonylamino group (a sulfonylamino group which may be substituted. For example, methanesulfonylamino group, benzenesulfonylamino group, 2-methoxy-5- group.
n-methylbenzenesulfonylamino group, etc.),

Alkoxycarbonylamino group (alkoxycarbonylamino group which may be substituted. For example, methoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group,
Benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.),

An aryloxycarbonylamino group (an optionally substituted aryloxycarbonylamino group, for example, a phenoxycarbonylamino group, a 2,4-nitrophenoxycarbonylamino group, etc.),

Alkoxycarbonyloxy group (alkoxycarbonyloxy group which may be substituted. For example, methoxycarbonyloxy group, t-butoxycarbonyloxy group, 2-benzenesulfonylethoxycarbonyloxy group, benzylcarbonyloxy group, etc.),

Aryloxycarbonyloxy group (optionally substituted aryloxycarbonyloxy group. For example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group, 4-t-butoxycarbonylamino group. Phenoxycarbonyloxy group, etc.),

Aminocarbonylamino group (optionally substituted aminocarbonylamino group. For example, methylaminocarbonylamino group, morpholinocarbonylamino group,
N-ethyl-N-phenylaminocarbonylamino group,
4-methanesulfonylaminocarbonylamino group),

An aminocarbonyloxy group (an optionally substituted aminocarbonyloxy group, for example, a dimethylaminocarbonyloxy group, a pyrrolidinocarbonyloxy group, a 4-dipropylaminophenylaminocarbonyloxy group, etc.),

Aminosulfonylamino group (optionally substituted aminosulfonylamino group. For example, diethylaminosulfonylamino group, di-n-butylaminosulfonylamino group, phenylaminosulfonylamino group, etc.),

A sulfonyloxy group (an optionally substituted sulfonyloxy group, for example, a phenylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group, a 4-chlorophenylsulfonyloxy group, etc.),

Further, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a halogen atom and the like can be mentioned.

More preferable groups among these are an alkoxy group, a halogen atom, an amino group, an acylamino group,
Examples thereof include a carbamoyl group, a sulfonylamino group, a sulfamoyl group and a carboxyl group.

Z ²² represents a mere bond or a divalent group for connecting X and Dye. Preferable examples of Z ²² include a bond, a carbonyl group, a sulfonyl group, a group having the same meaning as the group described for X, a carbonyl group, a sulfamoyl group, an acylamino group, a sulfonylamino group, an oxygen atom, a sulfonylaminosulfonyl group, Examples thereof include groups bound by a sulfonylaminocarbonyl group, a carbonylaminosulfonyl group, and the like. Of these, more preferred is a mere bond.

Next, Y will be described. Y represents a divalent group for connecting A and X. As a preferable example of Y, when A is a negative acting group represented by A-1 to A-4, —NHSO ₂ — is most preferable, in which case A is a nitrogen atom and X is a sulfur atom. To do. Also A
Are represented by A-8 to A-10 (JP-A-62-215).
In the case of positive-working groups (described in U.S. Pat. No. 270, U.S. Pat. No. 4,783,396), -O- and -S- are most preferred.

Further, m and n represent an integer of 1 or more. It is preferably an integer of 1 to 3, more preferably m = n =
It is 1.

Specific examples of the compound represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0098]

[Chemical 15]

[0099]

[Chemical 16]

[0100]

[Chemical 17]

[0101]

[Chemical 18]

[0102]

[Chemical 19]

[0103]

[Chemical 20]

[0104]

[Chemical 21]

[0105]

[Chemical formula 22]

[0106]

[Chemical formula 23]

[0107]

[Chemical formula 24]

[0108]

[Chemical 25]

[0109]

[Chemical formula 26]

Next, synthetic examples of the compound of the present invention will be shown. (1) Synthesis of specific compound example 1. (i) Synthesis of Intermediate, Sodium 2-morpholino-5-nitrobenzenesulfonate (A) 130 g of sodium 2-chloro-5-nitrobenzenesulfonate was dissolved in 200 ml of water and 130 ml of morpholine.
Heated to reflux for hours. After the reaction, the reaction solution is saturated saline solution 500
The precipitated crystals were collected by filtration, washed with 50 ml of saturated saline solution, and dried with a blow dryer. Thus, 127 g (yield: 82%) of intermediate (A) was obtained.

(Ii) Synthesis of intermediate, 2-morpholino-5-nitrobenzenesulfonic acid chloride (B) 31 g of intermediate (A) was suspended in 120 ml of acetonitrile and heated to reflux. 150g phosphorus oxychloride
Was slowly added dropwise, and then the mixture was heated to reflux for 6 hours. After completion of the reaction, the mixture was allowed to cool, poured into 600 ml of ice water, and the precipitated crystals were collected by filtration, washed with water, and dried with a blow dryer. Thus, 19.9 g (yield: 65%) of intermediate (B) was obtained.

(Iii) Synthesis of Intermediate (C) It was prepared according to the method described in JP-A-59-60434. Compound (D) 63.4 g is DMAC 200 ml
And α-picoline (30 ml) were added and the reaction system was placed under a nitrogen atmosphere. Under water cooling, 35.3 g of the intermediate (B) was added separately until the reaction temperature did not rise suddenly, and then the reaction was continued for 3 hours under water cooling. After the reaction is completed, the reaction solution is cooled to 500
The precipitated crystals were collected by filtration. The obtained crude crystals were recrystallized with 300 ml of acetonitril to obtain 64 g of intermediate (C).
(Yield 88%) was obtained.

[0113]

[Chemical 27]

[0114]

[Chemical 28]

(Iv) Synthesis of Intermediate (E) Reduced iron was obtained by adding 18.3 g of iron powder, 0.9 g of ammonium chloride,
It was prepared from 12 ml of water and 210 ml of 2-propanol and heated under reflux. To this, 60 g of the intermediate (C) was dividedly added so that a rapid reaction did not occur. After the addition, the mixture was heated to reflux for 3 hours. After the completion of the reaction, iron was filtered with Celite while hot. Water (500 ml) and n-hexane (50 ml) were poured into the filtrate, and the precipitated crystals were collected by filtration, washed with water and naturally dried. Thus, 53.5 g (yield: 93%) of intermediate (E) was obtained.

[0116]

[Chemical 29]

(2) Synthesis of Specific Compound Example 1 105.3 g of the intermediate (E) was dissolved in 500 ml of DMAC, 44.3 ml of α-picoline was added, and the reaction system was placed under a nitrogen atmosphere. Under water cooling, acid chloride (F) 93.5
g was added separately in 5 portions. After the addition, the reaction was carried out for 3 hours under water cooling. After completion of the reaction, 2.0 liter of methanol was poured and the mixture was heated to 50 ° C. To this, 25 ml of concentrated hydrochloric acid was added, and 175 ml of water was further added. After that, crystals are precipitated by slowly cooling with water. After the crystals were sufficiently precipitated, they were collected by filtration and washed with methanol to obtain 170 g of the specific compound example (1) (yield 87.9%).

[0118]

[Chemical 30]

Physical Properties of Specific Compound Example 1 ¹ H-NMR (DMSO-d ₆ ) δ 11.45 (br, S, 1H), 10.96 (S, 1
H), 9.21 (S, 1H), 88.8 (S, 1H),
8.28 (S, 2H), 7.97 (d, 1H), 7.8
8 (d, 1H), 7.70 (S, 2H), 7.57
(M, 2H), 7.42 (d, 1H), 7.26 (d,
1H), 6.74 (S, 2H), 6.60 (S, 1
H), 3.73 (br, S, 6H), 3.62 (br,
S, 4H), 3.30 (br, S, 4H), 3.23.
(S, 3H), 2.77 (br, S, 4H), 1.81
~ 1.20 (m, 36H), 0.83 (t, 3H),
0.55 (S, 9H),

In the light-sensitive material of the present invention, the dye-donor compound of the present invention, that is, the compound of the formula [I], may be used for magenta, and other conventionally known dye-donor compounds may be used.

The dye-donor compound used in combination is represented by the following general formula [I
I] can be used. General formula [II] 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, it is roughly classified into a negative type compound which becomes diffusive in the silver developed area and a positive type compound which becomes diffusible in the undeveloped area.

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 described in JP-A-2-32335, page (15), upper right column, line 18 to the same, page (15), lower left column 2,
It 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. For representative examples of Y, positive compounds, compounds of other types, etc., JP-A-2-32335, page (16), upper left column to the same (1)
7) The information up to the 7th line in the lower right column of the page applies.

When the dye-donor compound used in the present invention and the dye used in combination are reducible dye-donor compounds, a reducing agent (sometimes described 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 Nos. 49 to 50 of US Pat. No. 4,500,626.
Column, Nos. 4,483,914, columns 30-31, No. 4,
330,617, 4,590,152, JP-A-6
0-140335, pages (17) to (18), ibid. 57.
-40245, 56-138736, 59-1
78458, 59-53831, 59-182.
No. 449, No. 59-182450, No. 60-1195.
55, 60-128436 to 60-1284
39, 60-198540, 60-181
No. 742, No. 61-259253, No. 64-2440.
No. 44, No. 62-131253 to No. 62-1312
Up to 56, 78 of EP 220,746A2
To page 96 and the like, there are electron donors and electron donor precursors. Combinations of various electron donors such as those disclosed in US Pat. No. 3,039,869 can also be used.

An electron transfer agent may be used when the dye-donor compound of the present invention is diffusion resistant or when the reducing agent used in combination with the dye-donor compound of the present invention that is reducible is diffusion resistant. .

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-donating compound of the present invention 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 through an electron transfer agent. good. For example, when a colored dye-providing compound is present in the lower layer of the silver halide emulsion layer, the reduction in sensitivity can be prevented.

The dye-donating compound of the present invention can be used in a diffusion transfer type color photographic light-sensitive material, and the developing / image-forming method is to develop the processing composition at around room temperature or supply a trace amount of water or heat. A method of incorporating a solvent and performing heat development can be adopted.

First, the color diffusion transfer method will be described. A typical form of a 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 It is a form that does not need to be peeled from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment 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 dye-donating substance-containing layer 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 processing can be completed in a bright place. If desired, a peeling layer may be provided at an appropriate position so that all or part of the light-sensitive element can be peeled off from the image-receiving element (for example, such an embodiment is disclosed in JP-A-56-6).
7840 and Canadian Patent 674,082).

In another embodiment of the laminate type which is peeled off, a layer having at least (a) 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. .
U.S. Pat. No. 3,730,71 describes a mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled from the image receiving element.
No. 8.

On the other hand, there are roughly two typical forms in which a photosensitive 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. Explaining these in detail, 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. , The photosensitive layer coated surface and the mordant layer coated surface do not face each other before the exposure is completed, but after the exposure is completed (for example, during the development process), the photosensitive layer coated surface is turned over and overlapped with the image receiving layer coated surface. .
After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly 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-described form. Among others, in a peel-free type 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. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the 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 color diffusion transfer type film unit, 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 (mordant layer). As the mordant, those known in the photographic field can be used. As a specific example thereof, British Patent 2,01
1,912, 2,056,101, 2,09
3,041, U.S. Pat. Nos. 4,115,124, 4,273,853, 4,282,305, JP-A-59-232340, 60-118834, and 60-128443. , Ibid. 60-122940, ibid. 6
It is described in gazettes such as 0-122921 and 60-235134.

In addition to the above, various additives can 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. JP-A-2-32335 discloses a processing composition such as a silver halide emulsion, a spectral sensitizing dye, an emulsion layer, a full-color multi-layered structure used in a color diffusion transfer method, a color diffusion transfer method film unit and its constituent layers. 17) Lower right column, page 8 to the same publication, lower right column, page 19 (20)
The contents up to the first 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 peeling material include, for example, JP-A-47-8237, JP-A-59-220727, JP-A-49-4653, US Pat. Nos. 3,220,835, 4,359,518, and JP-A-49. -4334, 56-65133, 45
-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746, 4,366,227 and the like can be used. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives. For example, hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. There are also various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins such as acetylated gelatin and phthalated gelatin can be used. Further, it is polyvinyl alcohol, polyacrylate, polymethylmethacrylate or a copolymer thereof. Of these, a cellulose derivative is preferably used as the peeling 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 peeling material. The organic polymer used in the present invention has an average particle size of 0.0
Examples of the polymer latex include polyethylene, polystyrene, polymethylmethacrylate, polyvinylpyrrolidone, and butylacrylate having a size of 1 μm to 10 μm. Here, as described below, air is contained inside and the outside is made of an organic polymer. It is preferred to use a light-reflecting hollow polymer latex containing material. The above light-reflective hollow polymer latex is disclosed in JP-A-61-1516.
It can be synthesized by the method described in No. 46.

Next, the heat development color diffusion transfer method will be described. In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. For example, there are combinations of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. For the photothermographic material, a protective layer,
Various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either 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 an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), JP-A-62-253159, JP-A-3-1.
No. 10555, No. 2-236546, No. 1-1677
Any of the silver halide emulsions described in No. 43, etc. can be used.

The silver halide emulsion may be used as it is without being post-ripened, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). 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.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, JP-A-59-111636 and JP-A-4-73
The mercapto compound and its metal salt described in JP-A No. 649, the acetylene compounds described in JP-A-62-87957 and JP-A-4-255845 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A 61-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or before or after the nucleation of silver halide grains according to US Pat. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the binder of the constituent layers of the light-sensitive material and the dye-fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (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.

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. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. 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, and more preferably 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, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in 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-61-161.
213,847, 62-260,153, U.S. Pat. No. 4,684,604, JP-A-1-269936.
U.S. Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
78, JP-A-49-129,536 and JP-A-56-15.
3, 336, 56-153, 342, etc.

The development inhibitor releasing redox compound of the present invention contains 1 × 10 ^{−6 to} 5 × 10 ⁻² per mol of silver halide.
It is used in an amount of 1 mole, more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mole. The development inhibitor releasing redox compound used in the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. , Dissolved in methyl cellosolve, etc. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, by a method known as a solid dispersion method, a powder of a development inhibitor-releasing redox compound is ball milled in water, a colloid mill,
Alternatively, they can be dispersed by ultrasonic waves and used.

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 that activates the development of the light-sensitive material and stabilizes the image at the same time can be used. Specific compounds preferably used are described in US Pat. No. 4,50.
0,626, columns 51-52.

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 applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. 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 to 59 and JP-A-61-8825.
No. 6, pages (32) to (41), mordants described in JP-A-6-61
Examples thereof include those described in Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting high molecular compound as described in No. 63,079 may be used. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is 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 peelability between the light-sensitive material and the dye-fixing element. Specifically, JP-A-62-253159 (2
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. 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) is 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. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, 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 compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is 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) to (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.
5272 (125)-(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 element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive material. . The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination. A fluorescent whitening agent may be used in the light-sensitive material and the dye fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive material. As an example, K. Veenkataraman edition `` The Chemistry of
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-143
Examples thereof include the compounds described in No. 752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. 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,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type 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 preferably, JP-A-3
The vinyl sulfone type hardener described in -114,043 is used.

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. 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. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive material and the dye fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal 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. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,511,493.
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 add a base and / or a base precursor to the dye fixing element in order to improve the storage stability of the light-sensitive material. In the present invention, European Patent Publication No. 210,660 and US Pat. No. 4,740,4
A combination of a sparingly soluble metal compound described in No. 45 and a compound capable of undergoing a complex forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound) is used. Specifically, JP-A-2-269,338 (2) to
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 terminators 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. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Specific examples of the compound include an acid precursor that releases an acid by heating, an electrophilic compound that causes a substitution reaction with a coexisting base by heating, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. . For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, as the support for the light-sensitive material and the dye fixing element, those which can withstand the processing temperature are used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide are further prepared from polypropylene. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, 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 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 with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, 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, the light sources described in US 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. Image exposure can also 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, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As the 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 above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. An image signal operated by using a computer represented by Signal, CG, 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 diffusion transfer of dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in No. 45544 and the like 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., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. 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 facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher 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 accelerating the 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 (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can 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 the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

In order to accelerate 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 light-sensitive 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 it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye fixing element in order to promote dye transfer.

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. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

Any of a variety of thermal development equipment 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, No. 62-259.
44, JP-A-3-131856, and JP-A-3-13185.
The device described in No. 1 etc. is preferably used.

[0175]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A method for preparing the emulsion (1) for the fifth layer will be described.

To a well-stirred aqueous solution having the composition shown in Table 1, the solutions I and II having the compositions shown in Table 2 were added over 10 minutes, and then the solutions III and IV having the compositions shown in Table 2 were added. Liquid 25
Added over minutes.

[0178]

[Table 1]

[0179]

[Table 2]

[0180]

[Chemical 31]

Immediately before chemical sensitization, 1% of the dye (a) was added.
50 cc of solution (mixed solvent of methanol: water = 1: 1) was added.

Washing with water, desalting (pH = 4.
Then, 22 g of gelatin was added, and the pH = 6.
After adjusting to 0 and pAg = 7.9, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are shown in Table 3.

The yield of the obtained emulsion was 630 g, and it was a monodisperse cubic emulsion having a coefficient of variation of 10.3%, and the average grain size was 0.21 μm.

[0184]

[Table 3]

[0185]

[Chemical 32]

[0186]

[Chemical 33]

[0187]

[Chemical 34]

[0188]

[Chemical 35]

[0189]

[Chemical 36]

A method for preparing the emulsion (2) for the third layer will be described.

To a well-stirred aqueous solution having the composition shown in Table 4, the solutions I and II having the composition shown in Table 5 were added over 18 minutes, and then the solutions III and IV having the composition shown in Table 5 were added. 24 liquid
Added over minutes.

[0192]

[Table 4]

[0193]

[Table 5]

Washing with water, desalting (pH = 3.
Then, 22 g of gelatin was added, and pH = 5.
9. After adjusting pAg to 7.8, chemical sensitization was performed at 70 ° C. During the chemical sensitization, 6.7 cc of a 1% methanol solution of dye (b) was added. The compounds used for the chemical sensitization are shown in Table 6.

The obtained emulsion had a yield of 645 g, was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and had an average grain size of 0.24 μm.

[0196]

[Table 6]

[0197]

[Chemical 37]

[0198]

[Chemical 38]

[0199]

[Chemical Formula 39]

A method for preparing the emulsion (3) for the first layer will be described.

To a well-stirred aqueous solution having the composition shown in Table 7, the solutions I and II having the composition shown in Table 8 were added over 18 minutes, and then the solutions III and IV having the composition shown in Table 8 were added. Liquid 25
Added over minutes.

[0202]

[Table 7]

[0203]

[Table 8]

Washing with water, desalting (pH = 4.
Then, 22 g of gelatin was added and pH = 7.
4, after adjusting to pAg = 7.6, it was chemically sensitized at 60 ° C. During the chemical sensitization, 7.5cc of a 0.2% methanol solution of dye (c) (p-toluenesulfonic acid 0.1N) was added.
Was added. The compounds used for the chemical sensitization are shown in Table 9.

The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0206]

[Table 9]

[0207]

[Chemical 40]

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

19.0 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 5% 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 zinc hydroxide dispersion. Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described.

A uniform solution having the composition shown in Table 10 and a uniform solution having the composition shown in Table 11 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. A dispersion of the magenta dye-donor substance (M-
Call 1).

[0211]

[Table 10]

[0212]

[Table 11]

A uniform solution having the composition shown in Table 12 and a uniform solution having the composition shown in Table 13 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is a dispersion of a cyan dye-donor substance (Cy-
Call 1).

[0214]

[Table 12]

[0215]

[Table 13]

A uniform solution having the composition shown in Table 14 and a uniform solution having the composition shown in Table 15 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is used as a yellow dye-donor dispersion (Y-
Call 1).

[0217]

[Table 14]

[0218]

[Table 15]

Next, a method for preparing a gelatin dispersion of an electron donor will be described.

A uniform solution having the composition shown in Table 16 and a uniform solution having the composition shown in Table 17 were prepared, mixed and stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of electron donors.

[0221]

[Table 16]

[0222]

[Table 17]

A light-sensitive material 101 having the constitution shown in Table 18 was prepared using these emulsions and dispersions of dye-donor compounds.

[0224]

[Table 18]

[0225]

[Table 19]

The support used at this time was a paper support having a thickness of 135 μm laminated with polyethylene.

[0227]

[Chemical 41]

[0228]

[Chemical 42]

[0229]

[Chemical 43]

[0230]

[Chemical 44]

[0231]

[Chemical formula 45]

[0232]

[Chemical formula 46]

[0233]

[Chemical 47]

[0234]

[Chemical 48]

[0235]

[Chemical 49]

[0236]

[Chemical 50]

[0237]

[Chemical 51]

[0238]

[Chemical 52]

[0239]

[Chemical 53]

[0240]

[Chemical 54]

[0241]

[Chemical 55]

[0242]

[Chemical 56]

[0243]

[Chemical 57]

[0244]

[Chemical 58]

Also, a dispersion of a magenta dye-donor substance was prepared by changing the dye-donor compound from the method for preparing a gelatin dispersion of the hydrophobic additive and changing the amount of the high boiling point solvent.

[0246]

[Table 20]

[0247]

[Chemical 59]

[0248] Except for changing the gelatin dispersion of the magenta dye-donor compound in the fifth layer from the light-sensitive material 101 to the gelatin dispersion of the magenta dye-donor compound shown in Table 20, the same procedure as in the light-sensitive material 101 was carried out. Photosensitive materials 102 to 103 shown in the table were prepared.

[0249]

[Table 21]

[0250]

[Table 22]

Next, a method for preparing the dye fixing material will be described. Dye fixing material R101 having the constitution shown in Table 22 was prepared.

[0252]

[Table 23]

[0253]

[Table 24]

[0254]

[Chemical 60]

[0255]

[Chemical formula 61]

[0256]

[Chemical formula 62]

Photosensitive materials 101 to 103 and PS paper manufactured by Fuji Photo Film Co., Ltd. were used as the image receiving materials, and Pictrography 3000 manufactured by Fuji Photo Film Co., Ltd. was used as an image recording apparatus. That is, using the laser exposure apparatus described in Japanese Patent Application No. 2-129625, exposure was carried out under the conditions shown in Table 23, and 11 cc / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and thereafter, The dye-fixing material and the film surface were superposed so that the film surface was in contact. Using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 83 ° C., after heating for 30 seconds, the image receiving material was peeled from the photosensitive material to obtain an image on the image receiving material. In addition, since the development conditions are forcibly changed, the temperature of the film that has absorbed water is 8
An image was obtained on the image receiving material in the same manner as above except that development was performed using a heat drum whose temperature was adjusted to 8 ° C. Density measurement is made by X-Light Co.
The reflection densities are measured using the above, and the fluctuation ranges of the maximum density and the minimum density under the above two conditions are respectively ΔDmax and Δ
It was set to Dmin. (The smaller the values of ΔDmax and ΔDmin, the less susceptible to changes in the developing conditions.) Further, the photosensitive material 20 described above.
1 to 209 were left at 50 ° C.-50% for 14 days, and then exposed and treated in the same manner. That is, the fluctuation range of the maximum concentration and the minimum concentration before and after standing for 14 days when the treatment was performed under the condition where the temperature was adjusted to 83 ° C. was compared.
(The smaller the values are ΔTDmax and ΔTDmin, the smaller the deterioration.) The results are shown in Tables 24 and 25.

[0258]

[Table 25]

[0259]

[Table 26]

[0260]

[Table 27]

From the above results, it can be seen that the light-sensitive material of the present invention is not easily affected by fluctuations in developing conditions, and is not easily deteriorated even when stored under forced conditions before processing.

Example 2 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (4) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 2 g of sodium chloride in 600 ml of water).
g and 30 mg of the chemical (A) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 26 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, with the liquid (III) in Table 26,
Solution (IV) was added simultaneously at an equal flow rate for 25 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 90 mg of the drug B were added to adjust pH to 6.2 and pAg to 7.7, and then the ribonucleic acid decomposition product 500 was obtained.
mg and trimethylthiourea 2 mg were added and optimally chemically sensitized at 60 ° C. for about 50 minutes, and then 4-hydroxy-6-methyl-
After 225 mg of 1,3,3a, 7-tetrazaindene, 64 mg of dye (d) and 500 mg of KBr were sequentially added, the mixture was cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0265]

[Table 28]

[0266]

[Chemical formula 63]

Photosensitive silver halide emulsion (5) [for green emulsion layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and 15 mg of chemical A were added and kept at 55 ° C)
The solution (I) and the solution (II) shown in Table 27 were simultaneously added thereto at an equal flow rate for 20 minutes. After 10 minutes, liquid (III) and (I
Solution V) was added simultaneously at an equal flow rate for 20 minutes. Also (III),
One minute after the addition of the liquid (IV) was completed, an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 95 ml of water, 18 of the dye (e)) was added.
(Containing 0 mg and kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate 1 mg and 4-hydroxy-6-methyl-1 were added. , 3,3a, 7-Tetrazaindene (47 mg) and chloroauric acid (0.6 mg) were optimally chemically sensitized at 68 ° C., and then antifoggant (3) (165 mg) was added, followed by cooling. Thus the average particle size 0.45
635 g of a monodisperse cubic silver chlorobromide emulsion having a size of μm was obtained.

[0269]

[Table 29]

[0270]

[Chemical 64]

Photosensitive silver halide emulsion (6) [for blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 630 ml of water, 0.3 g of KBr: 2 g of NaCl, chemical A)
(15 mg was added and kept at 75 ° C.), solution I and solution II having the composition shown in Table 28 and solution II were added, and after 30 seconds, solution II was added over 30 minutes each, and II 5 minutes after the addition of the solution, add the solution III, and 30 seconds later, add the solution IV 3 times each.
Added over 0 minutes. Then I of the composition shown in Table 28
Solution II and solution IV were added over 35 minutes. Thereafter, 19 cc of a 1N solution of sodium hydroxide was added for neutralization to adjust the pH of the solution to 6. Then, add sodium thiosulfate to 1.
Add 4 mg and after 3 minutes add 1.2 mg of chloroauric acid for 60 minutes at 75 ° C
Kept at. Then, 430 mg of dye (f) was added to methanol 8
A solution dissolved in 0 cc was added, and 5 minutes later, the temperature was lowered to 35 ° C.

Thereafter, the solution v was added over 5 minutes.
Then, after washing with water and desalting by a conventional method (performed with 1 g of the precipitating agent (b) at pH 3.9), 6 g of lime-treated ossein gelatin and 68 mg of the antifoggant (4) were added to adjust the pH.
Was adjusted to 6.0. pAg is 8.5, electrical conductivity is 4
It was 000 μS. The silver halide grains of the resulting emulsion were octahedral and the grain size was 0.4 μm.

[0273]

[Table 30]

[0274]

[Chemical 65]

The zinc hydroxide dispersion was prepared in the same manner as in Example 1.

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. 7.3 g of cyan dye-donor compound (B), 10.6 g of cyan dye-donor compound (C), 0.8 g of surfactant (1), 1.03 g of electron donor (1), 7 g of high-boiling solvent (1), 3 g of high-boiling solvent (2), and 0.23 g of antifoggant (1) were weighed and added with 50 ml of ethyl acetate and dissolved by heating at about 60 ° C to form a uniform solution. . This solution, 71 g of a 14% solution of lime-processed gelatin and 80 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After the dispersion, 180 cc of water for dilution was added. This dispersion is referred to as a cyan dye-donor compound dispersion (Cy-4).

The magenta dye-donating compound (A) was added to 1
4.93 g, surfactant (1) 0.384 g, electron donor (3) 0.48 g, high boiling solvent (1) 7.4.
g and 0.21 g of the antifoggant (1) were weighed, 50 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 71% of this solution and 14% of lime-processed gelatin
g and 100 cc of water with stirring, and then 1 with a homogenizer
Dispersed for 0 minutes at 10,000 rpm. After that, 120 cc of dilution water was added. This dispersion is referred to as a dispersion (M-4) of the magenta dye-donor compound.

[0278]

[Chemical formula 66]

The yellow dye-donor compound (D) was added to 1
9.0 g: 3.8 g of compound (1), surfactant (1)
Of 1.74 g and the high boiling point organic solvent (2) of 9.7 g are weighed, 50 ml of ethyl acetate is added, and the mixture is heated and dissolved at about 60 ° C.,
A homogeneous solution was obtained. 14 of this solution and lime-processed gelatin
% Of 71% solution and 73 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After that, 105 cc of water for dilution was added. This dispersion is referred to as a yellow dye-donor compound dispersion (Y-4).

10 g of the electron donor (2), 3 g of the surfactant (1), 6.3 g of the high boiling point solvent (2), 1 ethyl acetate.
6 g was heated and dissolved at 60 ° C. to obtain a uniform solution. This solution and 71.4 g of 14% acid-treated gelatin were mixed with 70.6 g of water, added to the solution kept at 55 ° C., stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as an electron donor dispersion.

By these, a photothermographic material 201 as shown in Table 29 was constructed.

[0282]

[Table 31]

[0283]

[Table 32]

The stabilizer here is the same as in Example 1.

[0285]

[Chemical formula 67]

[0286]

[Chemical 68]

[0287]

[Chemical 69]

[0288]

[Chemical 70]

[0289]

[Chemical 71]

Further, a magenta dye-donor compound dispersion was prepared by changing the magenta dye-donor compound from the method for preparing a gelatin dispersion of the hydrophobic additive and changing the amount of the high boiling point solvent.

Photosensitive material 201 to first layer, third layer, fifth layer
Third layer using gelatin dispersion of dye-donor compound
Photosensitive materials 202 to 203 shown in Table 31 were prepared in exactly the same manner as the photosensitive material 201 except that the gelatin dispersion of the dye-providing compound shown in Table 0 was used. The image-receiving material and the dye-fixing material were prepared in the same manner as in Example 1.

[0292]

[Table 33]

[0293]

[Table 34]

Next, the above light-sensitive materials 201 to 203 were subjected to the following exposure and processing. Using a tungsten bulb, B.
G / R three-color separation filter (R: 600-700 nm,
A bandpass filter of G: 500 to 590 nm and B: 400 to 490 nm was used. ) And exposed at 1/10 "at 2500 lux. Fountain solution was supplied to the exposed emulsion surface with a wire bar, and then PS Paper PS-SG manufactured by Fuji Photo Film Co., Ltd. was used as an image receiving material. The materials were superposed so that the film surface was in contact with each other, and after the heat development temperature was heated at 83 ° C. for 30 seconds, the image receiving material was peeled off from the photosensitive material to obtain an image on the image receiving material. An image was obtained on the image receiving material in the same manner as described above except that development was carried out using a heat drum whose temperature was adjusted so that the water-absorbed film had a temperature of 88 ° C. in order to change the density. Vessel X-
The reflection density was measured using the light 404, and the fluctuation range of the maximum density and the minimum density under the above two conditions was calculated as Δ.
Dmax and ΔDmin. (The smaller the values of ΔDmax and ΔDmin are, the less susceptible to fluctuations in developing conditions.) Further, the above-mentioned photosensitive materials 301 to 309 were left to stand at 50 ° C.-50% for 14 days and then processed in the same manner. The fluctuation range of the maximum density and the minimum density of ΔTDmax and ΔTD, respectively
set to min. (The smaller the values of ΔTDmax and ΔTDmin, the less the deterioration.) The above results are shown in Tables 32 and 33.

[0295]

[Table 35]

[0296]

[Table 36]

From the above results, it can be seen that the light-sensitive material of the present invention is not easily affected by fluctuations in developing conditions, and is not easily deteriorated even when stored under forced conditions before processing.

Example 3 The magenta dye-donor compound of Example 2 was prepared according to US Pat. No. 39.
A light-sensitive material 301 was prepared in exactly the same manner except that the specific compound (1) described in No. 54476 was used. The dye-providing compound was replaced with an equimolar amount.

The dye fixing material was prepared in the same manner as in Example 1. Next, the above-mentioned photosensitive material 301 and (the photosensitive material of Example 2) 203 were exposed and processed in exactly the same manner as in Example 2.

The above results are shown in Tables 34 and 35.

[0301]

[Table 37]

[0302]

[Table 38]

[0303]

[Chemical 72]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masato Yamada 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A silver halide light-sensitive material comprising a support and a magenta dye-donating compound represented by the following general formula (1). General formula (1) In the formula, A represents a group having the property of immobilizing the magenta dye-donating compound of the general formula (1) in the light-sensitive material and cleaving the AL bond in the processing reaction after exposure. Dye
Represents a magenta dye group or a magenta dye precursor group. L represents a divalent linking group substituted with a cyclic amino group, and these may have a substituent. m and n are 1
Represents the above integers.