JP3227040B2 - Diffusion transfer type silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diffusion transfer type silver halide photographic material which gives a black transfer dye image. More specifically, the present invention relates to a black dye-donating substance which gives an imagewise diffusible black dye after development processing.

[0002]

2. Description of the Related Art Conventionally, several methods for forming a black-and-white image by diffusing and transferring a dye have been known. For example, Japanese Patent Publication No. 3-78617 discloses a method in which three color-donating substances of yellow, magenta and cyan are used in combination. Japanese Patent Application Laid-Open No. 3-296746 discloses a method in which two kinds of dye-donating substances, orange and blue, are used in combination. However, in a system using a plurality of these dye-donating substances in combination, it is necessary to add a large amount of the dye-donating substance to the light-sensitive material in order to obtain a high-density transfer image, and it is also necessary to add silver halide and other additives. Is also required in large quantities, and there are great restrictions on the design of the photosensitive material. Further, a method of forming and transferring a black dye at the time of development is disclosed in JP-A-3-260,645, and a method of utilizing a dye-donating substance which releases a black-colored dye is disclosed in JP-B-3-45820. . However, in a system for transferring these black dyes, it is extremely difficult to obtain neutral black under various light sources, and the molecular extinction coefficient of the dye is small, and in order to obtain a high-density transferred image, Again, a large amount of a dye-providing substance, silver halide, and other additives had to be added to the light-sensitive material. Further, in the image forming method using diffusion transfer, the transferred dye is usually fixed by a cationic mordant in the image receiving layer, but the above black dye has a low pKa that can generate a stable anionic species essential for dye fixing. It had an essential problem of not having a dissociable group.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a black dye-providing substance which can provide a high transfer density with a small amount of addition. A second object of the present invention is to
An object of the present invention is to provide a black dye-donating substance which gives a neutral black transfer image under any light source. A third object of the present invention is to provide a black dye-donating substance which releases an anionic black dye stably fixed by a mordant.

[0004]

The above object is achieved by the following (1).
~ (2). (1) Corresponds to silver halide having an image-like latent image or
Conversely, a dissociable OH group having a pKa of 6.0 or less, NH
Black having at least one group or COOH group
Releases pigmentRepresented by the following general formula (I)Dye donating
Diffusion transfer halogenation characterized by containing a substance
Silver photographic photosensitive material.General formula (I) Y- [GX-｛(L ¹ -Dye ¹ )-(L ^Two -Dye ^Two )-・ ・ ・-(L ^m -Dye ^m )｝ _n ] _p In the formula, Y corresponds to silver halide having a latent image in the form of an image or
Are the dye components before and after the reaction with the silver halide in reverse.
Represents a group having the property of causing a difference in the diffusivity of
L and G each represent a simple bond or a linking group. m and n are 1 or more
Represents a natural number above, p represents 1 or 2, and p is 2
GX-｛(L ¹ -Dye ¹ )-(L ^Two -Dye ^Two )-・ ・ ・-(L ^m -Dye ^m )
｝ _n May be the same or different, and m is 2 or more
When above, m-(L-Dye) are the same or different
When n is 2 or more, n (L ¹ -Dye ¹ )-(L ^Two -Dy
e ^Two )-・ ・ ・-(L ^m -Dye ^m ) May be the same or different
No. Dye represents a dye portion. Where p = m = n = 1
Except in cases.  (2) In the general formula (I), p = 1, m = 1 and n
= 2 or p = 1, m = 2 and n = 1
(1). A diffusion transfer type silver halide photographic light-sensitive material as described in (1).

Hereinafter, the black dye-donor substance of the present invention will be described in detail. The black dye-providing substance of the present invention is characterized in that a plurality of independent dye parts of the black dye are connected by a covalent bond. That is, from 400 nm to 7
The visible region of 00 nm is covered by a plurality of different dye conjugated systems, and since they are linked to each other, there is an advantage that only one functional redox site for providing an imagewise diffusible dye in the development process is required. Have. As a result, the amount of the dye-providing substance added can be reduced, and at the same time, the amount of silver halide, reducing agent, and the like can be reduced.

The degree of freedom in selecting a dye conjugate system for covering the entire visible region is large. For example, three dye conjugate systems of yellow, magenta, and cyan can be linked. Further, two dye conjugate systems (for example, red and cyan, green and magenta, and blue and yellow) which have a complementary color relationship with each other can be connected. Further, a dye conjugate system having a secondary absorption may be used, and a dye conjugate system having an insufficient absorption may be connected to the dye conjugate system. In order to reduce the amount of the dye-donating substance added, it is desirable to connect two dye conjugate systems having as low a molecular weight as possible and a large molecular extinction coefficient. It is also desirable to adjust the absorption maximum, broaden the absorption, adjust the molecular extinction coefficient, etc. to obtain a neutral black color.

The black dye-providing substance of the present invention has at least one dissociable group having a pKa of 6.0 or less in the released black dye molecule. Examples of the dissociable group having a pKa of 6.0 or less include a phenolic hydroxyl group, an enol hydroxyl group, an imide group, a sulfonamide group to which an electron withdrawing group is bonded, and a carboxyl group. Is preferably a phenolic or enol hydroxyl group or imide group having a pKa of 5.0 or less.

In the present invention, the dye-providing substance represented by the above general formula (I) is preferably used. In the general formula (I), p = 1, m = 1, n = 2 or p = 1, m = 2,
A dye-providing substance where n = 1 is used.

Next, each group of the compound of the formula (I) will be described. First, Dye will be described.

Dye represents a dye moiety having a single conjugated double bond skeleton. Examples of Dye include various known dyes. For example, there are yellow, magenta, and cyan dyes described in U.S. Pat. No. 4,783,396. In addition, known dyes having a hue such as blue, green, red, and orange can be used.
Specific examples are shown below, but the present invention is not limited thereto.

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In the formula (I), X is 2 when n = 1.
When n = 2, a trivalent (ie, n + 1) benzene ring or naphthalene ring is preferable, and these may have a substituent. Further, as another preferably used group, a heterocyclic ring containing one or two nitrogen atoms, which may have a substituent, and another ring which may be condensed (for example, pyrrole, pyrazole, Imidazole, pyrroline, pyrazoline, imidazoline, pyrrolidine, pyrazolidine, imidazolidine, indole, indoline, pyridine, pyrimidine, pyrazine, piperidine, pyridone adenine, tetrahydropyrimidine, morpholine, quinoline, quinoxaline, N-methylmorpholine, oxindole, hydantoin, etc.) Is mentioned. Another preferred group includes a chain or cyclic alkylene group having 2 to 10 carbon atoms, and a group partially containing an oxygen atom or a sulfur atom can also be used.

Among them, more preferred groups include a benzene ring, a naphthalene ring and a chain or cyclic alkyl group having 2 to 6 carbon atoms. Further, in view of easiness of synthesis and versatility, a benzene ring is preferred. And a naphthalene ring is most preferred.

When X has a substituent, preferred groups include an alkyl group and an aralkyl group (optionally substituted alkyl and aralkyl groups such as methyl, trifluoromethyl, benzyl, chloromethyl and dimethyl). 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, iso-butyl, sec-butyl, t-butyl,
n-benzyl group, sec-pentyl group, t-pentyl group,
Cyclopentyl, n-hexyl, sec-hexyl, t-hexyl, cyclohexyl, n-octyl, sec-octyl, t-octyl, n-decyl, n-undecyl, n-dodecyl , 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 (optionally substituted alkenyl group; 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 (optionally substituted aryl group; for example, phenyl, naphthyl, 3-hydroxyphenyl, 3-chlorophenyl, 4-acetylaminophenyl, 2-methanesulfonyl-4-nitrophenyl) , 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc.),

Heterocyclic group (optionally substituted heterocyclic group; for example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 5-nitro-2-pyridyl group, 3-pyridyl group,
3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazoline-2- Yl, morpholyl, etc.),

Acyl group (optionally substituted acyl group such as 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 (optionally substituted sulfonyl group; for example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, 4-
Toluenesulfonyl group, etc.),

Carbamoyl group (optionally substituted carbamoyl group; for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, etc.);

Sulfamoyl group (optionally substituted sulfamoyl group; 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 such as methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, 2-methoxyethoxycarbonyl group, etc.);

An alkoxy or aryloxysulfonyl group (optionally substituted alkoxy or aryloxysulfonyl group such as methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, 2-methoxyethoxysulfonyl group, etc.);

An alkoxy or aryloxy group (an optionally substituted alkoxy or aryloxy group;
For example, a methoxy group, an ethoxy group, a 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.),

An amino group (optionally substituted amino group such as amino group, methylamino group, N, N-dimethoxyethoxyamino group, methylphenylamino group, etc.);

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

Acylamino group (optionally substituted acylamino group; for example, acetylamino group, 2-carboxybenzoylamino group, 3-nitrobenzoylamino group,
3-diethylaminopropanoylamino group, acryloylamino group, etc.),

Acyloxy group (optionally substituted acyloxy group, for example, acetoxy group, benzoyloxy group, 2-butenoyloxy group, 2-methylpropanoyloxy group, etc.);

Sulfonylamino group (optionally substituted sulfonylamino group; for example, methanesulfonylamino group, benzenesulfonylamino group, 2-methoxy-5-
n-methylbenzenesulfonylamino group),

Alkoxycarbonylamino group (optionally substituted alkoxycarbonylamino group; for example, methoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group,
Benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.),

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

An alkoxycarbonyloxy group (optionally substituted alkoxycarbonyloxy group, for example, methoxycarbonyloxy group, t-butoxycarbonyloxy group, 2-benzenesulfonylethoxycarbonyloxy group, benzylcarbonyloxy group, etc.);

Aryloxycarbonyloxy group (optionally substituted aryloxycarboniooxy group; for example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group, 4-t-butoxycarbonyl Aminophenoxycarbonyloxy group),

Aminocarbonylamino group (optionally substituted aminocarbonylamino group; for example, methylaminocarbonylamino group, morpholinocarbonylamino group,
An N-ethyl-N-phenylaminocarbonylamino group,
4-methanesulfonylaminocarbonylamino group),

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

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

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

And carboxyl, sulfo, cyano, nitro, hydroxyl, and halogen atoms.

Among these groups, more preferred are an alkoxy group, a halogen atom, an amino group, an acylamino group,
A carbamoyl group, a sulfonylamino group, a sulfamoyl group, and a carboxyl group.

G is Y and X, L is X and Dye or two Dyes, and any group can be used as long as it can stably maintain the bond in the light-sensitive material. Preferred groups are -O- and-. _{NH -, - SO 2 -,} - CO-, a phenylene group, substituted phenylene group, a methylene group and the two
Examples include groups obtained by combining two or more valence residues. Two Dye (Dye ^m-1 and Dye ^m) is based on L ^m which connects a group to keep the independence of each of the π-conjugated system of the Dye ^m-1 and Dye ^m (say changing insulation between each of the π-conjugated system if to group), for example -NHCO- group, -NHSO ₂ - containing group.

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

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

As Y classified as a negative-acting releaser, a group of releasers that release a photographically useful group from an oxidized product is known. Preferred examples of this type of Y include the following formula (Y-1). (Y-1)

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In the formula, β represents a group of nonmetallic atoms necessary for forming a benzene ring, and the benzene ring may be condensed with a saturated or unsaturated carbocyclic or heterocyclic ring. α is-
Represents OZ ² or -NHZ ^3, wherein Z ² represents a group resulting hydroxyl group by a hydrogen atom or hydrolysis, Z
³ represents a hydrogen atom, an alkyl group, an aryl group, or a group that produces an amino group by hydrolysis. Z ¹ may have a substituent, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, a sulfonyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, Represents a sulfamoyl group, a ureido group, a urethane group, a heterocyclic group or a cyano group, a halogen atom, a is a positive integer, and when a is 2 or more, Z ¹ may be the same or different. . For formula (Y-1), -G is -N
HSO is a group represented by ₂ Z ⁴ Z ⁴ represents a divalent group.

Preferred groups among the groups contained in (Y-1) are (Y-2) and (Y-3). (Y-2)

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(Y-3)

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In the formula, Z ² and G have the same meanings as described in (Y-1). Z ⁵ and Z ⁶ represent an alkyl group, an aryl group, or an aralkyl group, and these may have a substituent. And Z
⁵ is a secondary or tertiary alkyl group, Z ⁵ and Z ⁶
Are preferably 20 or more and 50 or less.

Examples of these are disclosed in US Pat.
No. 28, 4,336,322, JP-A-51-113
No. 624, No. 56-16131, No. 56-71061
No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, No. 57-40
No. 43, No. 59-60, 439, JP-B-56-176
No. 56 and No. 60-25780.

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

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In the formula, α, G, Z ¹ and a have the same meanings as described in (Y-1). β ′ represents a group of nonmetallic atoms necessary for forming a benzene ring, and the benzene ring may be condensed with a saturated or unsaturated carbon ring or heterocyclic ring.

In the group represented by (Y-4), α is -OZ
² , wherein β ′ forms a naphthalene skeleton. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

As a releaser which releases a photographically useful group by the same reaction as (Y-1) and (Y-2), JP-A-51-104343, JP-A-53-46730 and JP-A-53-46730,
-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.
The groups described in No. 4 are exemplified.

The compound which releases a photographically useful group from the oxidized product by another reaction mechanism is represented by the formula (Y-5) or (Y-
The hydroquinone derivative represented by 6) is mentioned. (Y-5)

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(Y-6)

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In the formula, β ′ is the formula (Y-4) and Z ² is the formula (Y-
Has the same meaning as described in 1) above, and Z ⁷ has the same meaning as Z ² ;
Z ⁸ represents a substituent or a hydrogen atom described for Z ¹ . Z ²
And Z ⁷ may be the same or different. An example of this type is described in U.S. Pat. No. 3,725,062.

The hydroquinone derivative releasers of this type also have a nucleophilic group in the molecule. Specifically, it is described in JP-A-4-93747.

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

The negative acting releaser is represented by the following formula (Y-7). (Y-7)

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

(2) Next, Y is a positive-acting releaser that releases a photographically useful group in reverse to development.

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

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

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

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In the formula, O represents an oxygen atom (that is, (Y-8)
W represents an oxygen atom), and Z ¹² represents an atomic group having a property of forming a heterocyclic ring containing an NO bond and breaking the Z ¹² -G bond following cleavage of the NO bond. Z ¹² may have a substituent or a saturated or unsaturated ring may be condensed. Z ¹³ represents —CO— or —SO ₂ —.

As a more preferred group of (Y-9), (Y-9)
-10). (Y-10)

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

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

Other positive-acting releasers that exhibit functions by being reduced include BEND compounds described in US Pat. Nos. 4,139,379 and 4,139,389, and British Patent No. 11,445. Gar listed in
quin compound, JP-A-54-126535, JP-A-57
-84453.

When using these reducible releasers typified by Y represented by (Y-8), a reducing agent is used in combination, but an LD containing a reducing group in the same molecule is used.
A compound is also mentioned. This is disclosed in US Pat. No. 4,551,4.
No. 23.

Some positive-acting releasers are contained in the light-sensitive material as a reductant and deactivate when oxidized during processing. Japanese Patent Application Laid-Open No. 51-63618 and U.S. Pat.
Fields compound described in No. 79 and JP-A-49-1116
No. 28, No. 52-4819, U.S. Pat. No. 4,199,3
No. 54, Hinshaw compounds.

An example of this type of Y is (Y-11). (Y-11)

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In the formula, Z ¹⁷ and Z ^{19 each} represent a hydrogen atom or a substituted or unsubstituted acyl group, alkoxycarbonyl group or aryloxycarbonyl group, and Z ¹⁸ represents an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group. Group, aryloxycarbonyl group, carbamoyl group, sulfonyl group, sulfamoyl group, Z ²⁰ , Z
²¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. Specifically, JP-A-62
-245,270 and 63-46450.

As a positive-acting releaser having another mechanism, a thiazolidine-type releaser can be mentioned. Specifically, it is described in U.S. Pat. No. 4,468,451.

Next, specific examples of the compound of the present invention will be shown, but the present invention is not limited thereto.

Specific compound examples

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PK of dye released from specific compound examples
The a value is shown in Table 22 below. pKa values Measurement conditions Solvent _{DMF 150ml H 2 O 147ml Buffer 3ml} · Buffer composition phosphate 0.98g boric acid 0.618g citric acid _{2.1 g Et 3 N 1.01 g 1NH} 2 SO 4 10 ml H 2 O up to 100 ml · titrant 1N-KOH ・ Concentration 3.3 × 10 ^-5 mol / L

The pKa value was determined by a spectrophotometric method. For dyes having a plurality of dissociable groups in one molecule, the minimum p
Only the Ka value is shown.

The minimum pKa values of the dyes released from other specific compound examples were measured in the same manner and found to be 6.0 or less.

Next, examples of the synthesis of specific compounds of the present invention will be shown. Specific Compound Example Synthesis of No. 3 Compound (a)

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203 g of 5-amino-1-hydroxy-2-naphthoic acid (a) was dissolved in 1.5 liter of DMAC and 88 ml of chloroacetyl chloride was stirred at room temperature.
Was added dropwise. After stirring for 1 hour, 3 liters of acetonitrile and 2 liters of water were added, and the mixture was stirred at room temperature for 2 hours. The precipitated crystals were filtered, washed with acetonitrile and dried. Gray crystals (b) were obtained. Yield 155 g Yield 55% Compound (b)

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150 g of compound (b) and 150 g of p-nitrophenol were suspended in 3 liters of dried benzene and refluxed. 7 ml of dimethylformamide is added to this mixture.
And thionyl chloride (78 ml) were added dropwise, and the mixture was refluxed for 1 hour.
The reaction solution was cooled to room temperature, and the precipitated crystals were filtered and washed with acetonitrile. Gray crystal (c) yield 170 g yield 79% Compound (c)

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Compound (d)

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160 g of compound (c) and 10 g of compound (d)
2 g was suspended in 800 ml of anisole and stirred at 150 ° C. for 1 hour using an oil bath. The reaction solution was cooled to room temperature, and the precipitated crystals were filtered and washed with acetonitrile. 160 g of off-white crystals (e) were obtained. 80% yield Compound (e)

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Dissolve 150 g of sodium hydroxide in 1.5 liters of water, and stir at room temperature while stirring 150 g of compound (e).
Was added in small portions. After the addition was completed, the reaction temperature was raised to 50 ° C., and the mixture was stirred for 1 hour. After the reaction vessel was cooled with water and the internal temperature was cooled to room temperature, 300 ml of acetic acid was added dropwise. The precipitated crystals were filtered and washed with water and acetonitrile. 8 pale yellow crystals (f)
5 g were obtained. Yield 67% Compound (f)

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M-benzenedisulfonyl chloride 103
g and 16 ml of pyridine are dissolved in 500 ml of DMAC, and the internal temperature is lowered to 10 ° C. or lower in an ice bath. 80 g of compound (f) in DMA
It was dissolved in 150 ml of C and slowly added dropwise to the acid chloride solution. After completion of the dropwise addition, the reaction solution was brought to room temperature and stirred for 30 minutes. The reaction solution was poured into 1 liter of water and extracted with 600 ml of ethyl acetate, and the ethyl acetate layer was concentrated under reduced pressure. 10 in concentrate
1 liter of an aqueous solution of sodium hydroxide at 50 ° C.
After stirring for 0 minutes and cooling the reaction solution to room temperature, 500 ml of ethyl acetate was added and the mixture was separated to discard the ethyl acetate layer. To the aqueous layer was added 500 ml of methyl cellosolve, and the internal temperature was cooled to 5 ° C. or lower using an ice / MeOH bath. Separately, a diazonium salt solution of 2-cyano-4-methanesulfonylaniline (containing 2.5 times the molar amount of the coupler) synthesized by the nitrosylsulfuric acid method was dropped into the coupler solution. After completion of the dropwise addition, the mixture was stirred at 5 ° C. or lower for 30 minutes, and the reaction solution was poured into 2 liters of saturated saline and left overnight. The precipitated crystals were filtered and sufficiently washed with methanol. 80 g of brown crystals (g) were obtained. (N
aCl 20g) Yield 29% Compound (g)

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80 g of compound (g) and 10 ml of DMAC,
A mixture of 400 ml of acetonitrile was stirred at room temperature, and 80 ml of phosphorus oxychloride was added dropwise thereto. The internal temperature was raised to 60 ° C., and the mixture was stirred for 2 hours. After the reaction solution was cooled to room temperature, it was poured into 2 liters of ice water little by little. The precipitated crystals were filtered and washed with acetonitrile. 52 g of brown crystals (h) were obtained. 86% yield Compound (h)

[0139]

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Compound (i)

[0141]

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Compound (i) (10 g) and sodium hydrogen carbonate (6 g) were dissolved in DMAC (50 ml), cooled to 10 ° C. in an ice water bath and stirred. 16 g of the compound (h) was added thereto and 10
Stirred at C for 2 hours. The reaction solution was poured into 500 ml of water, and the precipitated crystals were filtered. The obtained crystals were added to 20 ml of DMAC.
, And 100 ml of methanol was added thereto and left at room temperature for 3 hours. The precipitated crystals were filtered, washed with methanol and dried. Specific compound example No. 3 10g was obtained. Brown crystal 40% yield

Synthesis of Specific Compound Example No. 18 Compound (j)

[0144]

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7.2 g of compound (j) and 6.0 g of sodium hydrogen carbonate were dissolved in 50 ml of DMAC, and the solution was dissolved in an ice-water bath.
The mixture was cooled to below ℃ and stirred. Compound (h) 1 was added to this solution.
6.0 g was added and stirred at room temperature for 1 hour. Reaction solution is 60
The crystals were poured into 0 ml of water and the precipitated crystals were filtered. The obtained crude crystals were separated and purified using silica gel column chromatography. (Eluent, methylene chloride / methanol = 4 /
1) 7.5 g of specific compound example No. 18 was obtained. Brown crystal 34% yield

In the light-sensitive material of the present invention, two or more dye-donating substances of the present invention may be used, or other conventionally known dye-donating substances may be used in combination. The dye-providing substance of the present invention can be used for a diffusion transfer type silver halide photographic light-sensitive material,
As the developing and image forming methods, a method of developing the processing composition at around room temperature, a method of supplying a small amount of water, or a method of performing thermal development by containing a thermal solvent can be adopted. The dye-providing substance of the present invention is preferably used for a photothermographic material.

Dye-donating substances are described in US Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 027. In this case, U.S. Pat. Nos. 4,555,470, 5,536,466, 4,536,467, 4,587,206, 4,555,476, and 4,464. High-boiling organic solvents such as those described in 599,296, JP-B-3-62,256 and the like can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-providing substance used. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39,853 and JP-A-51-59,943.
JP-A-62-286, a dispersion method using a polymer described in
No. 30,242 or the like, and a method of adding it as a fine particle dispersion can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the dye-providing substance in the hydrophilic colloid, various surfactants can be used. For example, those mentioned as the surfactants described in Research Disclosure, pages (37) to (38) of JP-A-59-157636, can be used.

[0148] The amount of the dye-providing materials of the present invention is arbitrary and is used usually in the range of ^{0.5g / m 2 ~20g / m 2} . Preferably from ^{1g / m 2 ~10g / m 2} .

The silver halide photographic light-sensitive material used in the present invention basically comprises a support having thereon a photosensitive silver halide emulsion, a dye-donating compound and a binder. Further, when used for a photothermographic material, an organic metal salt oxidizing agent and the like can be contained as necessary. These components are often added to the same layer, but they can also be added in separate layers. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is preferably incorporated in the photosensitive material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing material or a processing composition described later.

In the light-sensitive material, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, and an antihalation layer may be provided between the silver halide emulsion layers and as the uppermost layer and the lowermost layer. Various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, a layer constitution as described in the above patent, an undercoat layer as described in US Pat. No. 5,051,335, JP-A-1-167,838,
Intermediate layers having a solid pigment as described in JP-A-61-20,943; JP-A-1-120,553;
Intermediate layers having a reducing agent or a DIR compound as described in U.S. Pat.
7,454,5,139,919;
An intermediate layer having an electron transfer agent as described in JP-A-35,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer in which these are combined can be provided. The support is preferably designed to have an antistatic function and to have a surface resistivity of 10 ¹² Ω · cm or less.

The silver halide emulsion which can be used in the present invention includes:
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Also,
A so-called core-shell emulsion in which the inside of the grains and the surface layer of the grains have different phases may be used, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and a method of mixing monodispersed emulsions and adjusting the gradation as described in JP-A-1-167,743 and JP-A-4,223,463 is preferably used. . The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. Any of those having such crystal defects, or composites thereof, and the like may be used. Specifically, US Pat. No. 4,500,626
No. 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17, 02
9 (1978), No. 17, 643 (1978
No. 18, 716 (November 1979), p. 648, No. 307, 105 (November, 1989), p. 863 to 865, JP-A-62-253,15.
No. 9, No. 64-13,546, JP-A-2-236,5
No. 46, No. 3-110, 555, "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkide)
s, Chemie etPhisique Photographique, Paul Montel, 196
7) Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, F
ocal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VLZelikman et al.,
Making and Coating Photographic Emulsion, Focal Pre
ss, 1964), etc., any of which can be used.

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

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, emulsions described in JP-A-2-236542, JP-A-1-116637 and JP-A-4-126629 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound or JP-B-47-1
An organic thioether derivative described in 1,386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

The other conditions are described in “Physics and Chemistry of Photography” by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel, 1967), Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chem).
istry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikm).
an et al., Making and Coating Photographic Emulsion,
Focal Press, 1964). That is, any of the acidic method, the neutral method, and the ammonia method may be used,
As a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used.
As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can also be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158, JP-A-55-142329). 124, U.S. Pat. No. 3,650,575). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-11055).
No. 5, Japanese Patent Application No. 4-75,798). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to give the photosensitive silver halide used in the present invention green sensitivity, red sensitivity and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. 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.
And sensitizing dyes described in JP-A-617-257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in these steps and known photographic additives which can be used in the light-sensitive material and the dye-fixing material of the present invention are described in RD Nos. 17, 643 and 1 described above.
No. 8,716 and Nos. 307, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer. 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyeing, page 650, left column, ultraviolet absorbers. 7. Dye image page 25 page 650 left column page 872 stabilizer 8. Hardening agent page 26 page 651 left column 874-875 Binder page 26 page 651 left column pages 873-874 10. plasticizer, page 27 page 650 right column page 876 lubricant 11. Coating aid, page 26-27 page 650 right column 875-876 surfactant 12. Static Page 27, 650, right column, pages 876 to 877 Inhibitor 13. Matting agent, pages 878 to 879

As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include those described in the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds of polyvinylpyrrolidone and acrylamide polymer saccharide are exemplified. No. 4,960,681.
No. superabsorbent polymers described in JP-A-62-245,260, etc., i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer each other vinyl monomers having Alternatively, a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable.The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin in which the content of calcium and the like is reduced according to various purposes. Is also preferred.

In the case of employing a system in which a small amount of water is supplied to perform thermal development, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. When the superabsorbent water-soluble polymer is used in the dye-fixing layer or its protective layer, it is possible to prevent the dye from being re-transferred 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 ,
In particular, it is suitable that the weight is 10 g or less, and more preferably 7 g to 0.5 g.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. U.S. Pat. No. 4,500,626 is an example of a reducing agent used in the present invention.
Nos. 49-50, 4, 839, 272, 4,
330,617, 4,590,152, 5,0
17,454,5,139,919, JP-A-60
Nos. 140, 335, pp. (17) to (18), ibid.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
Nos. 0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181,742, No. 61-259,253
Nos. 62-201,434 and 62-244,04
Nos. 4, 62-131, 253, 62-131, 2
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
Nos. 2-234, 158 and 3-160, 443
And reducing agents and precursors described in EP-A-220,746 at pages 78 to 96 and the like. Various combinations of reducing agents, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, in order to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138,556 and 3-102,345 are used. Further, a method of stably introducing the compound into the layer as described in JP-A-2-230143 or JP-A-2-23504 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols,
No. 110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, compounds described as electron donors, and a non-diffusible and reducing dye described later. Donor compounds and the like. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Further, the above-mentioned reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixing, improvement of color reproduction, improvement of white background, and prevention of silver transfer to the dye fixing material. Specifically, European Patent Publication No. 52
4,649,357,040, JP-A-4-24
9,245, 2-64,633, 2-46,4
No. 50 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication No. 3-63,733,
JP-A-1-150,135, 2-110,557
And JP-A-2-64,634, JP-A-3-43,735, and EP-A-451,833. In the present invention, the total amount of the reducing agent is 0.01 to 20 mol per mol of silver,
Particularly preferably, it is 0.1 to 10 mol. Hydrophobic additives such as a dye-providing compound and a diffusion-resistant reducing agent can be introduced into a layer of a photothermographic material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
Nos. 36,466, 4,536,467 and 4,58
7,206, 4,555,476 and 4,59
No. 9,296, Japanese Patent Publication No. 3-62,256 and the like.
It can be used in combination with a low boiling organic solvent of 60 ° C. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating compound used. In addition, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc per 1 g of the binder
The following are appropriate: In addition, Japanese Patent Publication No. 51-39,853,
A dispersion method using a polymer described in JP-A-51-59,943 or a method of adding a fine particle dispersion described in JP-A-62-30,242 can also be used.
In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing a hydrophobic compound in a hydrophilic colloid,
Various surfactants can be used. For example, those mentioned as the surfactants described in Research Disclosure, pages (37) to (38) of JP-A-59-157636, can be used.

In the photothermographic material of the present invention, a compound which activates development and stabilizes an image at the same time can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In a system in which an image is formed by diffusion transfer of a dye, an unnecessary dye or coloring matter is fixed or made colorless in the constituent layers of the photothermographic material of the present invention to improve the white background of the obtained image. Various compounds can be added. Specifically, EP-A-353,741
No. 461,416, JP-A-63-163,345.
And the compounds described in JP-A Nos. 62-203,158 can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with the photothermographic material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. The relationship between the photosensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
No. 88,256, pages (32) to (41),
Mordants described in U.S. Pat. Nos. 4,774,162 and 4,619,883.
And Nos. 4,594,308 and the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The binder used in the dye fixing material of the present invention is preferably the above-mentioned hydrophilic binder. Further, it is preferable to use a combination of carrageenans as described in EP-A-443,529 and a latex having a glass transition temperature of 40 ° C. or lower as described in JP-B-3-74,820. Auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer can be provided on the dye fixing material as needed. It is particularly useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a slipper or an agent for improving the releasability between the photosensitive material and the dye-fixing material. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective. Also, silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are effective.

An anti-fading agent may be used in the photothermographic material or the dye fixing material. Examples of the anti-fading agent include antioxidants, ultraviolet absorbers, and certain metal complexes. Dye image stabilizers and ultraviolet absorbers described in Research Disclosure are also useful. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Unexamined Patent Publication No.
The compounds described in -159,644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681), and benzophenone-based compounds (Japanese Unexamined Patent Publication No. 2,784), and JP-A Nos. 54-48,535 and 62-1.
36, 641 and 61-88, 256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155 and 4,245.
No. 018, columns 3-36, No. 4,254,195, No. 3
Columns 8 to 8, JP-A-62-174,741 and JP-A-61-8
8, 256, pp. 27-29, pp. 63-199,
No. 248, JP-A Nos. 1-75,568 and 1-74,2
No. 72 and the like.

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or the dye may be supplied from outside such as a photothermographic material or a transfer solvent described later. It may be supplied to the fixing material. The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination. A fluorescent whitening agent may be used in the photothermographic material or the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photothermographic material or a transfer solvent. For example, K. Veenkataraman ed., "The Chemis
tryof Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
No. 143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers, and fluorescent whitening agents are described in JP-A-62-21527.
No. 2, pages 125 to 137, JP-A-1-161,
No. 36, pages (17) to (43).

Examples of the hardener used in the constituent layers of the photothermographic material and the dye-fixing material include the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042, 1984-116,655
Nos. 62-245,261 and 61-18,942
And hardening agents described in JP-A-4-218,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane),
N-methylol hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be used. These hardeners are
0.001 to 1 g, preferably 0.005 to 0.5 g, is used per 1 g of gelatin applied. The layer to be added may be any of the constituent layers of the dye-fixing material for the photosensitive material, or may be added in two or more layers.

In the constituent layers of the photothermographic material or the dye fixing material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13546 (7). Pages (9), (57) to (71) and (8)
1) to (97), U.S. Pat. No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No. 63-264,747, JP-A-1-150,1
No. 35, No. 2-110, 557, No. 2-178, 65
No. 0, RD 17, 643 (1978) (24)-(2
5) Compounds described on page and the like. These compounds are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver.

The constituent layers of the photothermographic material and the dye-fixing material include coating aids, improved releasability, improved slipperiness, antistatic properties,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are described in the aforementioned Research Disclosure, JP-A-62-173463, and JP-A-62-173463.
183,457. The constituent layers of the photothermographic material and the dye fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-209.
No. 44, 62-135826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as a fluorine oil or a solid fluorine compound resin such as an ethylene tetrafluoride resin described in No. 62-135826, etc. No.

In the photothermographic material and the dye fixing material, a matting agent can be used for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin and polymethacrylate, and JP-A-63-2747 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
Nos. 44 and 63-274952.
In addition, the compounds described in the aforementioned Research Disclosure can be used. These matting agents are the top layer (protective layer)
In addition, it can be added to the lower layer as needed. In addition, the constituent layers of the photothermographic material and the dye fixing material may contain a thermal solvent, an antifoaming agent, a germicide / antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32),
No. 11,338 and Japanese Patent Publication No. 2-51,496.

In the present invention, an image formation accelerator can be used in the photothermographic material and / or the dye fixing material. Examples of the image formation accelerator include a redox reaction between a silver salt oxidizing agent and a reducing agent, promotion of a reaction such as formation of a dye from a dye-providing substance or decomposition of the dye or release of a diffusible dye, and photothermographic exposure. It has the function of promoting the transfer of the dye from the material layer to the dye fixing layer, and from the physicochemical function, a base or base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant , Silver, or compounds that interact with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40. As base precursors, salts of organic acids and bases that decarboxylate by heat, intramolecular nucleophilic substitution,
There are compounds that release amines by Rossen rearrangement or Beckmann rearrangement. An example is U.S. Pat.
Nos. 514,493 and 4,657,848.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, a method in which a base and / or a base precursor is contained in a dye-fixing material is preferable from the viewpoint of improving the storage stability of the photothermographic material. . In addition to the above,
EP 210,660, U.S. Pat. No. 4,74
No. 0,445, and combinations of compounds which can form a complex with metal ions constituting the hardly soluble metal compound (referred to as complex forming compounds), and JP-A-61-232,451. Compounds that generate a base by electrolysis described in (1) can also be used as the base precursor. In particular, the former method is effective. It is advantageous to add the hardly soluble metal compound and the complex forming compound separately to the photothermographic material and the dye fixing material as described in the above-mentioned patent.

In the present invention, various development stoppers can be used in the photothermographic material and / or the dye fixing material for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. . The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For more details, see
2-253, 159, pages (31) to (32).

In the present invention, as a support for the photothermographic material or the dye fixing material, a support that can withstand the processing temperature is used. In general, papers and synthetic polymers (films) described in the Photographic Society of Japan, "Basics of photographic engineering-silver salt photography-", published by Corona Co., Ltd. (1979), pp. 223-240. And photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further, Film-processed synthetic paper made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. Is used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue, and carbon black as necessary. In addition, JP-A-62-253,159, pages (29) to (31), JP-A-1-161,236, pages (14) to (17), and JP-A-63-316,848.
JP-A-2-22,651, JP-A-3-56,955
And the supports described in U.S. Pat. No. 5,001,033. The back surface of these supports may be coated with a support binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent. Specifically, JP-A-63-22024
No. 6, etc. can be used. The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder.

Examples of a method of exposing and recording an image on a photosensitive material include a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and the like. Using a copier exposure device to scan and expose the original image through slits, etc., image information via electric signals, light emitting diodes, various lasers (laser diodes,
A method of performing scanning exposure by emitting light from a gas laser or the like (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application No. 3-338
Nos. 82, 4-9, 388, 4-281, 442), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., directly or There is a method of exposing through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source and the like, JP-A-2-53,37.
No. 8, No. 2-54, 672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of expressing nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (K
DP), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives,
For example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) are preferably used. As a form of the wavelength conversion element, a single-coupled optical waveguide type, a fiber type, and the like are known, and any of them is useful. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTS).
C) TV signals, image signals obtained by dividing an original image into a number of pixels such as a scanner, image signals created using a computer represented by CG and CAD, and X-ray diagnosis using an imaging plate Medical image signals from an apparatus, a tomography apparatus (MRI) using nuclear magnetic resonance, a tomography apparatus (CT) using X-rays, or an ultrasonic diagnostic apparatus can be used.

The photothermographic material and / or dye fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is described in JP-A-61-14.
No. 5,544 and the like can be used. The heating temperature in the heat development step is about 50 ° C. to 250 ° C., and particularly about 60 ° C. to 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the case of the latter, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is particularly 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.
Up to lower temperatures are preferred.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50 ° C. to 100 ° C. Examples of the solvent used for accelerating the development and / or for diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are described in the section of the image formation accelerator). Described are used), a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer, and any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up or circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
The device described in No. 5, etc. or water may be used.

These solvents can be applied to the photothermographic material, the dye fixing material, or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of applying this water,
For example, the methods described in JP-A-62-253,159 (page 5) and JP-A-63-85,544 are preferably used. In addition, the solvent is enclosed in the microcapsule,
It can also be used in the form of a hydrate incorporated in advance in the photothermographic material or the dye fixing element or both. The temperature of the water to be applied may be 30 ° to 60 ° C. as described in JP-A-63-85,544. In particular, it is useful to keep the temperature at 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the photothermographic material and / or the dye fixing material may be employed. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but is preferably a dye fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and heterocycles therefor.

As a heating method in the development and / or transfer step, a heating block, a plate, a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far infrared lamp heater may be used. For example, or a method of passing through a high-temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

In the processing of the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
Nos. 5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application No. 4-277,517, 4
Devices described in JP-A-243,072 and JP-A-4-244,693 are preferably used. Further, as a commercially available apparatus, a Pictrostat 100, a Pictrostat 200, a Pictography 3000, a Pictography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.

Example 1 The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

A method for producing a photosensitive silver halide will be described. Photosensitive silver halide emulsion Solution (I) and solution (II) having the composition shown in Table 2 were simultaneously added to the well-stirred aqueous solution having the composition shown in Table 1 over 13 minutes, and 10 minutes later, Solutions (III) and (IV) having the compositions shown in Table 2 were added over 33 minutes.

[0189]

[Table 1]

[0190]

[Table 2]

[0191]

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Also, 150 cc of a 0.35% aqueous solution of the sensitizing dye (a) was added over a period of 27 minutes from 13 minutes after the start of the addition of the solution III.

[0193]

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After washing with water and desalting (using a precipitant (a) at a pH of 4.1) according to a conventional method, 22 g of lime-treated ossein gelatin was added, the pH was 6.0, and the pAg was 7. After adjusting to 9, it was chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 3. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm. When the reflection spectrum of the emulsion was measured, sharp absorption having a peak at 680 nm was measured.

[0195]

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[0196]

[Table 3]

[0197]

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[0198]

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A method for preparing a gelatin dispersion of colloidal silver will be described. The solution having the composition shown in Table 5 was added to the well-stirred aqueous solution having the composition shown in Table 4 over 24 minutes. Then, after washing with water using the sedimentation agent (a), 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 512 g
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0200]

[Table 4]

[0201]

[Table 5]

Next, examples of the black dye donating compound of the present invention (N
o.18) A method for preparing a gelatin dispersion will be described.

A gelatin dispersion of the black dye-donating compound example (No. 18) was prepared according to the formulation shown in Table 6. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution. The aqueous phase component heated to about 60 ° C. was added to this solution, followed by stirring and mixing, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.

[0204]

[Table 6]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 7. That is, after mixing and dissolving each component, the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.25
μm was used. )

[0206]

[Table 7]

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

[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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Using the above, a photothermographic material 100 shown in Table 8 was prepared.

[0214]

[Table 8]

[0215]

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[0216]

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[0219]

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The light-sensitive material 101 was prepared by using 1024 mg / m ² of the black dye-donating compound (No. 21) in place of 1141 mg / m ² of the black dye-donating compound (No. 18) used in the first layer of the light-sensitive material 100. With a black dye-donating compound (N
o.22) Photosensitive material 102 was prepared using 1243 mg / m ² .

Next, a method for producing an image receiving material will be described. A dye-fixing material 100 having the structure shown in Table 9 was produced.

[0220]

[Table 9]

[0221]

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[0222]

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[0223]

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The photothermographic materials 100, 101 and 102 and the dye fixing material 100 obtained as described above were exposed as follows using a digital color printer "Fujix Pictography PG-3000" manufactured by Fuji Photo Film Co., Ltd.・ Processed. As the image information, information obtained from an X-ray diagnostic apparatus FCR4000 using an imaging plate manufactured by Fuji Photo Film Co., Ltd. was used. Exposure was performed using semiconductor laser light having an oscillation wavelength of 680 nm under the exposure conditions shown in Table 10. The exposed photosensitive material was immersed in water kept at 40 ° C. for 2.5 seconds, squeezed with a roller, and immediately superimposed so that the dye fixing material and the film surface were in contact with each other. Next, the temperature of the water-absorbing membrane surface was 8
Using a heat drum whose temperature has been adjusted to 5 ° C,
When the dye-fixing material was peeled off by heating for 0 second, a black-and-white image having a clear color and a color tone suitable for medical use was obtained from the dye-fixing material. The visual density (the highest density <Dmax> and the lowest density <Dmi> of the transmission image obtained on the dye fixing material 100 using the density meter X-light 404 manufactured by X-Light Co., Ltd.
n>). The results are shown in Table 13 below. A neutral black image could be obtained at a sufficient maximum density and a low minimum density.

[0225]

[Table 10]

Comparative Example 1 A method for preparing a gelatin dispersion of a hydrophobic additive will be described. A gelatin dispersion of a yellow dye-donating compound, a magenta dye-donating compound, and a cyan dye-donating compound in the same manner as the gelatin dispersion of the black dye-donating compound (No. 18) except that the materials shown in Table 11 are used. Was prepared.

[0227]

[Table 11]

[0228]

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[0229]

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[0230]

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The light-sensitive material 100 was prepared in the same manner as in the light-sensitive material 100 except that the gelatin dispersion of the black dye-donating compound (No. 18) in the first layer was replaced by a gelatin dispersion of cyan, magenta and yellow dye-donating compounds. In the same manner, photosensitive materials 110 shown in Table 12 were prepared.

[0232]

[Table 12]

The obtained light-sensitive material 110 and the dye-fixing material 100 used in Example 1 were exposed and processed in the same manner as in Example 1, and the visual densities shown in Table 13 (maximum density <Dmax)
> And minimum density <Dmin>).

[0234]

[Table 13]

Example 2 In addition to the gelatin dispersion and the photosensitive silver halide emulsion used in Example 1, the following were prepared.

A method for preparing a dispersion of an electron transfer agent will be described. 10 g of the following electron transfer agent, 20 g of a 2% aqueous solution of carboxymethylcellulose as a dispersant, and 0.2 g of a surfactant were added to 70 g of a 7% aqueous gelatin solution, and milled for 60 minutes using glass beads having an average particle size of 0.75 mm. did. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle size of 0.35 μm.

[0237]

[Table 14]

[0238]

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Next, a method for preparing a dye trapping agent dispersion will be described. The following polymer latex (solid content 13%)
While stirring a mixture of 108 ml, 20 g of surfactant and 1232 ml of water, 600 ml of 5% aqueous solution of surfactant was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Next, 1500 ml of water was added and the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0240]

[Table 15]

[0241]

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Next, a method for preparing a gelatin dispersion of the black dye-donating compound (No. 3) will be described. Except for using the materials shown in Table 16, the black dye-providing compound of Example 1 (No. 1) was used.
It was prepared similarly to the gelatin dispersion of 8).

[0243]

[Table 16]

[0244]

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[0245]

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[0246]

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Using the above materials, photosensitive materials 200 shown in Table 17 were prepared.

[0248]

[Table 17]

[0249] Instead of a black dye-donor compound 552 mg / m ² of the first layer and the third layer of photosensitive material 200, a black dye-donor compound (No.7) 501mg / m ² photosensitive material 201 using
Was used to prepare a light-sensitive material 202 using 526 mg / m ² of a black dye-donating compound (No. 9).

The photothermographic materials 200, 201, and 202 obtained as described above and the dye fixing material 100 used in Example 1 were used in the same manner as in Example 1 by using a digital color printer manufactured by Fuji Photo Film Co., Ltd. Exposure and processing using “PG-3000”, and Table 2 below
A neutral black transfer image having the highest density and the lowest density shown in FIG. 1 was obtained. However, as the image information, a tomographic apparatus using nuclear magnetic resonance, which is obtained by so-called MRI, is used, and in the processing, a heat drum whose temperature is adjusted so that the temperature of the water-absorbing film surface becomes 83 ° C. Using.

Comparative Example 2 A method for preparing a gelatin dispersion of a hydrophobic additive will be described.

A yellow dye-donating compound, a magenta dye-donating compound and a cyan dye were prepared in the same manner as in the gelatin dispersion of the black dye-donating compound (No. 18) in Example 1 except that the materials shown in Table 18 were used. A gelatin dispersion of the donor compound was prepared.

[0253]

[Table 18]

[0254]

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[0255]

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[0256]

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[0257]

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Next, a method for producing the photosensitive material 210 will be described. In the same manner as in Table 19, except that gelatin dispersions of yellow, magenta, and cyan dye-donating compounds were used instead of the gelatin dispersions of the black dye-donating compounds in the first and third layers of the photosensitive material 200, respectively. The photosensitive material 21 shown
0 was created.

[0259]

[Table 19]

[0260]

[Table 20]

The photothermographic material 210 obtained as described above and the dye fixing material 100 used in Example 1 were exposed and processed in the same manner as in Example 2 to obtain the highest density and the lowest density shown in Table 21. A neutral black transfer image was obtained.

[0262]

[Table 21]

As shown in Table 8, Table 12, Table 13, Table 17, Table 19 and Table 21, by using the black dye-donating compound of the present invention, the dye-donating substance, halogen Neutral black images could be obtained at high maximum densities despite the greatly reduced use of silver halide and other additives.

Table 2 shows the pKa value of the black pigment of the present invention.
2 is shown.

[0265]

[Table 22]

[0266]

EFFECT OF THE INVENTION By using the black dye-donating compound of the present invention, a neutral black image having a sufficiently high maximum density can be obtained by using less dye-donating substance, silver halide and other additives as compared with the conventional method. Was obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-66249 (JP, A) JP-A-6-167792 (JP, A) JP-A-6-507259 (JP, A) (58) Survey Field (Int. Cl. ⁷ , DB name) G03C 8/40 503

Claims (2)

(57) [Claims] 1. A dissociable OH having a pKa of 6.0 or less corresponding to or inversely corresponding to silver halide having an image-like latent image.
Transfer-type halogen containing a color-donating substance represented by the following general formula (I) that emits a diffusible black dye having at least one group, NH group or COOH group: Silver halide photographic material. General formula (I) Y- latent in ^{[GX - {(L 1 -Dye} 1) - (L 2 -Dye 2) - - ··· (L m -Dye m)} n] in _{the p-type} Y is imagewise Compatible with silver halide with image
Are the dye components before and after the reaction with the silver halide in reverse.
Represents a group having the property of causing a difference in the diffusivity of
L and G each represent a simple bond or a linking group. m and n are 1 or more
Represents a natural number above, p represents 1 or 2, and p is 2
GX-｛(L ¹ -Dye ¹ )-(L ² -Dye ² )-・ ・ ・-(L ^m -Dye ^m )
｝ _N may be the same or different and m is 2 or more
When above, m-(L-Dye) are the same or different
When n is 2 or more, n (L ¹ -Dye ¹ )-(L ² -Dy
e ² )-・ ・ ・-(L ^m -Dye ^m ) may be the same or different
No. Dye represents a dye portion. Where p = m = n = 1
Except in cases. 2. In the general formula (I), p = 1 and m = 1
And n = 2, or p = 1, m = 2 and n
= 1 a diffusion transfer type silver halide photographic material of claim 1, wherein.