JP3233516B2 - Thermal transfer dye-providing material using pyrazolopyrimidin-7-oneazo dye, silver halide photosensitive material using compound releasing the dye, and novel pyrazolopyrimidin-7-oneazo dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the use of pyrazolopyrimidin-7-one azo dyes having excellent absorption properties, having high fastness to light, heat, air and chemicals, and having high transferability.
The present invention relates to a method of use, particularly to a diffusion transfer type silver halide photosensitive material.

[0002]

2. Description of the Related Art An azo dye is a diazonium salt, a so-called diazonium salt, prepared from a compound having active hydrogen, a so-called coupler component such as phenols and p-dialkylaminobenzenes, and an aminoaryl compound or an aminoheteroaromatic compound. A dye formed by azo coupling with a component. The azo dye can be selected from various structures for the coupler component and the azo component, and thus has a wide variety of color tones, and is a typical dye among the dyes. Among them, pyrazolotriazole azo dyes, aminopyrazole azo dyes, pyridone azo dyes, diaminopyridine azo dyes, etc. are known as those having a heterocyclic coupler component.

In recent years, color electrophotography, ink jet type color copying, thermal transfer type color copying, printing ink, diffusion transfer type silver halide photography, and the like have been actively studied, and azo dyes have been used as dyes for image formation. .
On the other hand, along with the development of electroimaging, the demand for filters for solid-state photographing tubes and color liquid crystal televisions has been increasing, and azo dyes have been studied as dyes for filters.

[0004]

However, conventionally known azo dyes still have problems to be solved.
For example, the absorption is not sufficiently sharp yet, and there are problems in color reproduction of an image and performance of a filter. In addition, the dye has insufficient fastness to light, heat, air, moisture, and chemicals, and has problems in image storability and filter durability. In addition, the synthesis was difficult and the cost was high.

[0005] To solve the above problems, the present inventor has
We conducted intensive research on azo dyes. As a result, it has been found that the azo dye containing pyrazolopyrimidin-7-one as a coupler component has sharp absorption, high fastness to light, heat, air, moisture, chemicals, and the like, and high heat transferability. Was.

Also, as a result of development under basic conditions,
A color diffusion transfer photographic method using an azo dye image forming compound which gives an azo dye having a diffusibility different from that of the image forming compound itself has been well known. The image forming compound (dye donating compound) used in this method also has drawbacks such as low transferability and low fastness of the image to be formed. The present invention improves this disadvantage.

An object of the INVENTION An object of the present invention is excellent in transcription of, the formed image light,
The purpose of this invention is to provide a silver halide photosensitive material for color diffusion transfer which has high resistance to heat, air, moisture, and chemicals.
You.

[0008]

The object of the present invention is to provide the following (1).
Thus it was achieved.

[0009]

[0010]

[0011]

(1) A silver halide photosensitive material comprising a support and a layer containing a dye-donating compound represented by the following general formula (II): General formula (II) (Dye-G) q-Y In the formula (II), G represents a mere bond or linking group which is cleaved in response to or in reverse development, and Y represents a latent image in an image form. Dye is released corresponding to or inversely corresponding to the photosensitive silver halide, and the released dye and (Dye-G) q −
Represents a group having such a property as to cause a difference in diffusibility with the compound represented by Y, and q is 1 or 2, and when q is 2, two Dye-Gs are the same or different. You may. Dye is a dye residue of pyrazolopyrimidine-7 On'azo dye residue represented by the following general formula (I) (where formula (I), the metal ion complexes
Does not change ).

[0013]

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In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, an acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group, silyloxy group, heteryloxy group, alkylthio Group, arylthio group, heterylthio group, carboxylic acid group and sulfonic acid group. These groups have further substituents
Is also good. Ar represents an aryl group or a heteroaromatic group derived from a diazo component, which may be substituted . However
And Ar has a substituent ortho to the azo group.
The substituent is -OH or a hydrolyzable precursor thereof.
There is no. R ² and R ³ may combine with each other to form a ring structure. Dye and G are represented by R ¹ , R ² , R in formula (I)
Bond at ³ or Ar.

[0015]

[0016]

[0017]

Hereinafter, the general formula (I) will be described in detail.

[0019]

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R ¹ , R ² and R ³ each independently represent a hydrogen atom, an aryl group, a heterocyclic group, an alkyl group, a cyano group, a carboxyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group , Acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, silyloxy group, heteryloxy Group, alkylthio group, arylthio group, heterylthio group, sulfonic acid group and the like.

Specific examples of R ¹ , R ² and R ³ include:
Hydrogen atom, carboxylic acid group, sulfonic acid group, aryl group (including those having a substituent; preferably 6 to 3 carbon atoms)
0, for example phenyl, m-acetylaminophenyl, p
-Methoxyphenyl), an alkyl group (including those having a substituent. Preferably, it has 1 to 30 carbon atoms, for example, methyl,
Ethyl, isopropyl, t-butyl, n-octyl, n
-Dodecyl), a cyano group, a carboxyl group, an acyl group (preferably having 1 to 30 carbon atoms, for example, acetyl, pivaloyl, benzoyl, furoyl, 2-pyridyl), a carbamoyl group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyl) , Ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl), an alkoxycarbonyl group (including those having a substituent, preferably having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonyl group ( It preferably has 7 to 30 carbon atoms, for example, phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), and an acylamino group [preferably Including those having an alkyl carbonyl amino group (substituent group having 1 to 30 carbon atoms. For example, formylamino, acetylamino, propionylamino,
Cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 30 carbon atoms (including those having a substituent. For example, benzoylamino, p-toluylamino,
Pentafluorobenzoylamino, m-methoxybenzoylamino), preferably a hetenylcarbonylamino group having 4 to 30 carbon atoms (including those having a substituent; for example, 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino) An alkoxycarbonylamino group (including those having a substituent; preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), and an aryloxycarbonylamino group (having a substituent It preferably has 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino, o-
Chlorophenoxycarbonylamino), a sulfonylamino group (preferably having 1 to 30 carbon atoms such as methanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), an aminocarbonylamino group (preferably having 1 to 30 carbon atoms such as methylaminocarbonylamino) , Ethylaminocarbonylamino, anilinocarbonylamino, dimethylaminocarbonylamino), a sulfamoylamino group (preferably having 1 to 30 carbon atoms, for example, methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino), an amino group (Including an anilino group, preferably having 0 to 30 carbon atoms, such as amino, methylamino, dimethylamino, ethylamino,
Diethylamino, n-butylamino, anilino), alkoxy group (including those having a substituent. Preferably, it has 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, isopropoxy, n-dodecyl. Oxy), an aryloxy group (including those having a substituent, preferably having 6 to 30 carbon atoms, for example, phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy), and a silyloxy group (preferably having 3 carbon atoms). -30, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, cetyldimethylsilyloxy, phenyldimethylsilyloxy),
Heteryloxy group (including those having a substituent; preferably having 3 to 30 carbon atoms, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), alkylthio group (having a substituent Preferably having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-butylthio, t-butylthio), an arylthio group (including those having a substituent, and preferably having 6 to 30 carbon atoms, for example, phenylthio); Heterylthio group (including those having a substituent; preferably having 3 to 30 carbon atoms, for example, 2-pyridylthio, 2- (1,
3-benzoxazolyl) thio, 1-hexadecyl-
1,2,3,4-tetrazolyl-5-thio, 1- (3-
N-octadecylcarbamoyl) phenyl-1,2,2
3,4-tetrazolyl-5-thio), a heterocyclic group (including those having a substituent. Preferably, it has 3 to 30 carbon atoms, for example, a group represented by the following chemical formula,

[0022]

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In the above heterocyclic group, R represents a hydrogen atom or a nonmetallic substituent, and n represents an integer of 0-4. R represents an alkyl group (including those having a substituent, having 1 to 30 carbon atoms), an aryl group (including those having a substituent, having 6 to 30 carbon atoms), and a heterocyclic ring (including those having a substituent). C2-C30), cyano group, alkoxy group (including those having a substituent; C1-C30),
An aryloxy group (including those having a substituent, having 6 to 30 carbon atoms), an acylamino group (1 to 30 carbon atoms), a carbamoyl group (1 to 30 carbon atoms), an oxycarbonyl group (2 to 30 carbon atoms), Preferred are an alkoxycarbonylamino group (including those having a substituent; 2 to 30 carbon atoms), an aryloxycarbonylamino group (7 to 30 carbon atoms), and an aminocarbonylamino group (1 to 30 carbon atoms).

R ² and R ³ may combine with each other to form a ring structure. Specific examples thereof include benzo-fused rings,
Pyrido condensed rings, pyrazolo condensed rings and the like can be mentioned.

Particularly preferred as R ¹ , R ² and R ³ are a hydrogen atom, an alkyl group, an aryl group, an acylamino group, a cyano group, a carbamoyl group, an alkoxycarbonyl group and a sulfamoyl group.

Ar represents an aryl group or a heteroaromatic group derived from a diazo component. Ar is preferably an aryl group [having 6 to 30 carbon atoms. It may be substituted by a substituent, and as the substituent, an alkyl group,
Alkoxy, aryloxy, acyloxy, aryl, halogen, aryloxycarbonyl, alkyloxycarbonyl, cyano, nitro, carbamoyl, acyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino Group, aminocarbonylamino group, sulfonyl group,
Sulfamoyl group, sulfonylamino group, amino group (including substituted amino group), hydroxy group and heterocyclic group]. Further, a heterocyclic group (2 to 30 carbon atoms) is also preferable. Preferred heterocyclic groups include imidazolyl, pyridyl, pyrazolyl, thiazolyl, benzoimidazolyl, quinolyl, benzopyrazolyl, benzothiazolyl, isothiazolyl, benzoisothiazolyl, pyridoisothiazolyl, and thiadiazolyl. Is mentioned.

A preferred specific example of Ar is C 6
~ 30 aryl groups such as p-methoxyphenyl,
m-methoxyphenyl, o-methoxyphenyl, p-chlorophenyl, m-chlorophenyl, o-chlorophenyl, p-nitrophenyl, p-cyanophenyl, p-
(N, N-diethyl) phenyl, 2,4-dichlorophenyl, m-chlorophenyl, p-tolyl, p-mesylphenyl, 3,4-dicyanophenyl, 4-methoxycarbonylphenyl, 2,4,6-trichlorophenyl ,
Heterocyclic groups having 2 to 30 carbon atoms, for example, groups shown below.

[0028]

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In the dye of the present invention, R ¹ is an alkyl group,
R ² and R ³ are each independently an alkyl group, an aryl group, an alkoxycarbonyl group, or an aminocarbonyl group which may be the same or different, and Ar is a substituted aryl group or a heteroaromatic group. Those which are group groups (that is, the dyes of the general formula (IV)) are completely new ones not conventionally known as dyes. These dyes had excellent performance that could not be expected from conventional knowledge. Its performance includes good hue, high molecular extinction coefficient, high robustness to light, moisture, heat, air, and chemicals, good transferability, and the like. Among these dyes, preferably, R ¹ is an alkyl group having 1 to 6 carbon atoms (including those having a substituent; for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl), An aryl group having 6 to 12 carbon atoms (including those having a substituent; for example, phenyl, p-methoxyphenyl, o-chlorophenyl, tolyl, and 2-naphthyl). R ² and R ³ may be each independently the same or different and include an alkyl group having 1 to 6 carbon atoms (including those having a substituent. For example, methyl, ethyl, n-butyl, n-
Propyl, isopropyl, t-butyl, n-hexyl), an aryl group having 6 to 12 carbon atoms (including those having a substituent. For example, phenyl, 3,5-dichlorophenyl, o-chlorophenyl, m-methoxyphenyl, p- −
Bromophenyl, naphthyl) and alkoxycarbonyl groups having 2 to 6 carbon atoms (including those having a substituent.
Methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, t-butoxycarbonyl), having 1 carbon atom
To 6 aminocarbonyl groups (including those having a substituent; for example, aminocarbonyl, N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N
-Butylcarbonyl). Ar is preferably a substituted aryl group having 6 to 12 carbon atoms (substituents include nitro, cyano, halogen, alkyl, alkoxy, alkylsulfonyl and the like. For example, p-nitrophenyl, p-
Cyanophenyl, 2-chloro-4-nitrophenyl, 2
-Mesyl-4-nitrophenyl, 2-mesyl-4-cyanophenyl, 2-cyano-4-nitrophenyl, 2,4
-Dichlorophenyl, m-chlorophenyl, p-methoxyphenyl, m-methoxyphenyl, p-tolyl, 2,
4,5-trichlorophenyl) and a heteroaromatic group having 3 to 10 carbon atoms (specific examples are those listed in Chemical formulas 8 and 9 above).

When Ar is an aryl group, it is preferably an aryl group substituted with an electron-withdrawing group.
Among them, an aryl group in which an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.3 or more is preferably substituted at the p-position of the azo value is preferable. The σ _p value is more preferably 0.45 or more,
The σ _p value is most preferably 0.60 or more.

When Ar is a heteroaromatic group, it is preferably a 5- or 6-membered heteroaromatic group containing at least one nitrogen atom. More preferably, the heteroaromatic group is substituted with an electron-withdrawing group.

Here, Hammett used in this specification
Is briefly described. Hammett's rule is Ben
Determine the effect of substituents on the reaction or equilibrium of zen derivatives
To discuss quantitatively, 1935 L. P. Provided by Hammett
This is a rule of thumb that has been widely accepted today.
Have been. Substituent constant determined by Hammett's rule
Is σ_pValue and σ_mThere are values, these values are many common
It can be found in a compendium, for example, A. Dean,
"Lange's Handbook of Chemistry" No. 12
Edition, 1979 (McGraw-Hill)
No. 122, pp. 96-103, 1979 (Nankodo)
New In the present invention, each substituent is substituted by Hammett.
Base constant σ_pIs limited or explained by
Is a substituent with a value known in the literature, which can be found in the above
It does not mean that it is limited only, its value is unknown in the literature
Even if it is measured based on Hammett's law
Needless to say, it also includes substituents that may be included in the box.
Nor. From now on, σ_pValue, σ _mThe value represents this meaning. C
With an electron-withdrawing group having a meth
Is an acyl group, an acyloxy group, a carbamoyl group,
Alkoxycarbamoyl group, aryloxycarbamoy
Group, cyano group, nitro group, alkylsulfinyl group,
Arylsulfinyl group, alkylsulfonyl group, ant
Sulfonyl group, sulfamoyl group, halogenated alcohol
Kill group, halogenated alkoxy group, aryl halide
Oxy group, halogenated alkylthio group, two or more σp
Aryl substituted with an electron-withdrawing group having a value of 0.15 or more
Groups and heterocycles.

The dye of the present invention may have an atomic group having an effect of suppressing fading in the dye molecule. It is particularly preferable when high fastness of an image is required. The atomic group having the effect of suppressing fading is represented by R ¹ ,
Any of R ² , R ³ and Ar may be bonded. An atomic group having an effect of suppressing fading is disclosed in JP-A-3-20.
The atomic groups described in Japanese Patent No. 5189 are effective.

Hereinafter, specific examples of the dye of the present invention will be described.

[0035]

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[0036]

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[0037]

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[0038]

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Of these, examples of those preferably used in the thermal transfer dye-providing material include 1 to 19 and 25 to 32. Diffusion transfer type silver halide photosensitive materials which are used by releasing from an image forming compound. Examples of those which are preferably used are 20 to 24.

The method for synthesizing the dye of the present invention will be described below. The dye of the present invention can be synthesized by subjecting compound A (coupler) and compound B (diazo component) to an azo coupling reaction.

[0041]

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Synthesis Example Synthesis of Compound 1

[0043]

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20 ml of ethanol, 1.0 g of compound C,
0.77 g of compound D and 2.0 g of sodium acetate were added, and 40
The reaction was performed at 30 ° C. for 30 minutes. After the reaction, hydrochloric acid was added to make the reaction solution acidic, and water and ethyl acetate were added to perform extraction. The extract was dried, the solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography to obtain 0.70 g of Compound 1.
Obtained. (Yield 47.3%) Compound 1 showed yellow in ethyl acetate. The dye compounds 1 to 32 can be easily synthesized in the same manner as in Synthesis Example 1.

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

Next, a silver halide light-sensitive material for color diffusion transfer using a dye-donating compound (image forming compound) which releases a dye of the present invention will be described. The dye-donating compound that releases the dye of the present invention is represented by the general formula (II). General formula (II) (Dye-G) _q- Y

G represents a mere bond or linking group which is cleaved corresponding to or opposite to development, and Y represents D corresponding to or inversely corresponding to a photosensitive silver halide having an image-like latent image.
ye, and the released Dye and (Dye-G) _q −
Q represents a group having a property that causes a difference in diffusibility with the compound represented by Y, and q represents 1 or 2
And when q is 2, the two Dye-Gs may be the same or different. q is preferably 1.

The image forming compound represented by the general formula (II) is preferably a compound represented by the following general formula (V).

[0083]

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In the formula (V), G and Y correspond to G and Y in the formula (II).
Is synonymous with Ar ′, R ¹ ′, R ² ′ and R ³ ′ are each a divalent group obtained by removing one hydrogen atom from the monovalent substituent represented by Ar, R ¹ , R ² and R ³ in the formula (I). Represents a substituent of p, r, s, and t are integers from 0 to 2, and p, r,
The sum of s and t is 1 or 2, and preferably 1. p
Is preferably 1, and r, s and t are preferably 0. When p, r, s or t is 0,-(GY) represents a hydrogen atom.

Hereinafter, G and Y will be described in detail. G
Is a simple bond or a divalent linking group that is cleaved corresponding to or opposite to development. When G is a divalent linking group, it is preferably an alkylene group, an arylene group, -O
-, - S -, - NR 4 -, - CO -, - SO 2 - or,
It is a group combining two or more of these. R ⁴ is a hydrogen atom or an alkyl group. The above divalent linking group is
Preferred among the G in combination of two or more are as follows. ^{_{-SO 2 NR 4 -, - CONR}} 4 -, - SO 2 NR 4 C
^{O -, - CONR 4 CO -} , - SO 2 NR 4 CO-,

[0086]

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[0087] R ⁴ is also hydrogen atom is A alkyl group. In the formulas (VI) and (VII), R ⁵ has the same meaning as R ^{1 in the} formula (I) , and n is an integer of 0 to 4. Hereinafter, Y will be described. The expression was described including G. (1) Examples of Y include a negative-acting releaser that releases a photographically useful group in response to development.

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

[0089]

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

Preferred groups among the groups included in (Y-1) include (Y-2) and (Y-3). (Y-2)

[0092]

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(Y-3)

[0094]

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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 described 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)

[0098]

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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.

A releaser which releases a dye residue by the same reaction as (Y-1) and (Y-2) is disclosed in
-104343, 53-46730, 54-1
No. 30122, No. 57-85055, No. 53-381
No. 9, No. 54-48534, No. 49-64436,
And the groups described in JP-B-57-20735, JP-B-48-32129 and JP-B-48-39165, and U.S. Pat. No. 3,443,934.

Compounds which release a dye residue from an oxidized product by another reaction mechanism include compounds represented by the formula (Y-5) or (Y-6)
And a hydroquinone derivative represented by (Y-5)

[0103]

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(Y-6)

[0105]

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

The hydroquinone derivative releasers of this type include those having a nucleophilic group in the molecule. Specifically, it is described in JP-A-4-97347.

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 includes the following formula (Y-7). (Y-7)

[0110]

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

(2) Next, examples of Y include a positive-acting releaser that releases a dye residue in reverse to development.

Examples of the positive-acting releaser include a releaser that 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)

[0114]

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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 - This N-W bond after EAG receives electrons represent cleaved. 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), preferred is a group represented by formula (Y-9). (Y-9)

[0117]

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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 the 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 —.

A more preferred group among (Y-9) is (Y-10). (Y-10)

[0120]

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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 or more carbon atoms.

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

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

When using these reducible releasers represented 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 are deactivated 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)

[0127]

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In the formula, Z¹⁷, Z¹⁹Is a hydrogen atom or
Or unsubstituted acyl group, alkoxycarbonyl group,
Z represents an oxycarbonyl group;¹⁸Is an alkyl group,
Reel group, aralkyl group, acyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
A sulfonyl group, a sulfonyl group or a sulfamoyl group;²⁰, Z
^{twenty one}Is a hydrogen atom or a substituted or unsubstituted alkyl group,
Represents a reel group or an aralkyl group. Specifically, JP-A-62
-245,270 and 63-46450.
You.

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. The releasers represented by the general formulas (Y-1) to (Y-11) are preferably resistant to diffusion. In that case,
The releasers (Y-1) to (Y-11) preferably have a diffusion-resistant group (a so-called ballast group). This is preferably a group containing a hydrophobic group of 8 to 32 carbon atoms. Such an organic ballast group may be directly or directly attached to the compound of the present invention, for example, an imino bond,
(A single bond or a combination of ether bond, thioether bond, carbonamide bond, sulfonamide bond, ureido bond, ester bond, carbamoyl bond, sulfamoyl bond, etc.). Examples of the ballast group include an alkyl group (eg, dodecyl group, octadecyl group, etc.), an alkoxyalkyl group (eg, 3- (octyloxy) propyl group, 3- (2-ethylundecyloxy) propyl group, etc.), Alkoxyaryl group (for example, 4- (n-octadecyloxy) phenyl group and the like).

The preferred image-forming compounds of the present invention are illustrated below, but the invention is not limited thereto.

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

The image-forming compound of the present invention can be easily synthesized by using a dye of the present invention as a raw material for synthesis by a known method.

The compound represented by the formula (II) is preferably used in the same layer as the silver halide emulsion or in a layer adjacent thereto. The amount used is 0.0 mol / mol silver.
1 to 5 mol, particularly 0.05 to 1 mol, is preferred.

The silver halide photosensitive material for color diffusion transfer using the image forming compound represented by the formula (II) will be described below. The light-sensitive material used in the present invention basically has a light-sensitive silver halide, a binder and a dye-donating compound (which may also serve as a reducing agent) on a support. These components are often added to the same layer, but may be added separately to another layer if they can react. 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.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. . For example, a combination 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, or a combination of a red-sensitive layer, a first infrared layer, and a second infrared layer and so on. Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. In photothermographic materials,
Various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer can be provided. (Basic Structure of Silver Halide Grains and Preparation Method) Silver halides usable in the present invention include silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide. However, silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing not more than 30 mol% of silver iodide are preferred. The silver halide emulsion used in the present invention may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging.
Further, so-called multi-structure grains having different halogen compositions between the inside and the grain surface may be used. Of the multiple structure grains, those having a double structure may be particularly referred to as a core-shell emulsion.

The silver halide used in the present invention preferably has a multi-structure grain, and a core-shell emulsion is more preferable. However, the present invention is not limited to this. The silver halide emulsion used in the present invention is preferably a monodispersed emulsion, and the coefficient of variation described in JP-A-3-110555 is preferably 20% or less. It is more preferably at most 16%, further preferably at most 10%. However, the present invention is not limited to this monodispersed emulsion.

The average grain size of the silver halide grains used in the present invention is from 0.1 μm to 2.2 μm, preferably from 0.1 μm to 1.2 μm. The crystal habit of the silver halide grains may be cubic, octahedral, high aspect ratio tabular, potato-shaped, or any other. More preferably, they are cubic emulsions.

Specifically, US Pat. No. 4,500,626, column 50, column 4628021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (197).
8) and any of the silver halide emulsions described in JP-A-62-25159 and the like can be used.

In the process of preparing the silver halide emulsion of the present invention, when a so-called desalting step for removing excess salt is performed, as a means for this purpose, gelling of gelatin, which has been known for a long time, is carried out by gelling with Nudel water. Method, and inorganic salts comprising polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, aliphatic acylated gelatin, aromatic A sedimentation method (flocculation) using acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Preferably, a sedimentation method using a compound represented by a sedimentation agent (a) or a sedimentation agent (b) described below is used, but the present invention is not limited thereto. An ultrafiltration method may be used without using any of the above settling agents. The removal of the excess salt may be omitted.

The silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and chromium for various purposes. These compounds may be used alone,
Also, two or more kinds may be used in combination. 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. Further, when it is contained, it may be uniformly contained in the particles, or may be localized on the surface or inside of the particles.

The preferred amount of iridium used in the present invention is from 10 ^-9 to 10 ^-4 mol, more preferably from 10 ^-8 to 10 ^-6 mol, per mol of silver halide. In the case of a core-shell emulsion, iridium may be added to the core and / or the shell. Compounds include K ₂ IrC
l ₆ and K ₃ IrCl ₆ is preferably used.

Further, the rhodium used in the present invention is preferably
The addition amount is 10 per mole of silver halide.^-9-10^-6Mo
It is. In addition, a preferable addition amount of iron used in the present invention.
Is 10 per mole of silver halide ^-7-10^-3In mole
And more preferably 10^-6-10^-3Is a mole. these
Silver chloride, silver chlorobromide, bromide
Pre-doping fine grain emulsions such as silver and silver iodobromide
Halogenation by adding this fine grain emulsion from
A method of locally doping the silver emulsion surface is also preferably used.
Can be In the stage of forming silver halide grains, halogen
Rodin salt, NH as a silver halide solvent_ThreeAnd the compounds described below
A tetra-substituted thioether compound as shown in the product (a) or
Organic thioether derivatives described in JP-B-47-11386
Or described in JP-A-53-144319.
A sulfur-containing compound or the like can be used. Silver halide
Japanese Patent Publication No. 46-7781 (JP-B-46-7781)
JP-A-60-222842, JP-A-60-122935
Add nitrogen-containing compounds as described in
Can be. The protective core used when preparing the emulsion of the present invention.
As a Lloyd and other hydrophilic colloid binders
It is advantageous to use gelatin,
Besides, hydrophilic colloids can also be used. For example
Gelatin derivatives, grafted polymers of gelatin and other polymers
Proteins such as mer, albumin, and casein;
Such as chill cellulose, cellulose sulfates, etc.
Cellulose derivatives; sodium alginate, starch derivatives;
Revinyl alcohol, polyvinyl alcohol Partial aceta
, Poly-N-vinylpyrrolidone, polyacrylic acid,
Polymethacrylic acid, polyacrylamide, polyvinyla
Single or common materials such as midazole and polyvinyl pyrazole
Use of a variety of synthetic hydrophilic polymer materials such as polymers
Can be.

Examples of the gelatin include lime-processed gelatin, acid-processed gelatin, Britain, and Society of Gelatin.
The Scientific, Photography of Japan (Bull. Soc. Sci. Phot., Japan), No. 16: Page
30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin may also be used.

For other conditions, refer to “Chemie et Physique Photographique” by P. Glafkides.
(Paul Montel, 1697),
GFDuffin, Photographic Emulsion Chemistry (Photographi
c Emulsion Chemistry) "(The Focal Press
The Making of Coating Photographic Emulsion, by VLZelikman et al., The Focal Press, 1966.
(The Focal Press, 1
964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any of a one-side mixing method, a double-mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.

Further, in order to accelerate grain growth, the addition concentration, amount or rate of silver salt and halogen salt to be added may be increased (Japanese Patent Application Laid-Open Nos. 55-142329 and 55-158124; U.S. Pat. No. 3650575).

During or after grain formation, the surface of the silver halide grains may be replaced with a halogen which forms sparingly soluble silver halide grains.

Further, the stirring method of 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. Preferred p
The range of H is 2.2 to 6.0, more preferably 3.0 to 6.0.
5.5.

The emulsion for the blue-sensitive layer used in the present invention is described in Japanese Patent Application No. 3-308225. A silver halide emulsion composed of silver halide grains having a layer with a high silver iodide content on the grain surface and chemically sensitized before desalting and adding iodide ions is particularly preferred.

(Method of Adding Sensitizing Dye) The method of adding the sensitizing dye may be basically any time. That is, at the beginning of the formation of silver halide emulsion grains (may be added before nucleation),
During or after formation, or at the beginning, during or after the desalting step, at the time of redispersion of gelatin, and before, during, during or after preparation of chemical sensitization, or during preparation of a coating solution. Preferably, it is added during or after the formation of silver halide grains, or before, during or after chemical sensitization. Addition after chemical sensitization means adding a sensitizing dye after all chemicals necessary for chemical sensitization have been added.

As described in US Pat. No. 4,183,756, before the formation of silver halide grains, they may be present in a reaction system between a soluble silver salt (for example, silver nitrate) and a halide (for example, potassium bromide). U.S. Pat.
As described in No. 25666, after the nucleation of silver halide grains and before the end of the step of forming silver halide grains, it may be present in the above-mentioned reaction system. A sensitizing dye may be present in the reaction solution simultaneously with the formation of the silver halide grains, that is, simultaneously with the mixing of the silver salt and the halide. It is more excellent in storability under high temperature conditions and in gradation.

The concentration of the additive solution, the solvent, the time of addition (may be added all at once or over time), temperature and pH
May be any condition. Either addition at the liquid surface or addition in the liquid may be used. These conditions are disclosed in
No. 10555 and the like.

(Types of Sensitizing Dyes) The sensitizing dyes used in the emulsion used in the present invention include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and the like. Hemioxonol dyes are included.

Specifically, US Pat. No. 4,617,257
JP-A-59-180550 and JP-A-60-14033
No. 5, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.

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. No. 3615641, JP-A-6
3-23145).

In the present invention, in any of the above addition methods, the total amount of the sensitizing dye may be added at one time.
Further, it may be added in several portions. Further, the sensitizing dye may be added in the form of a mixture with a soluble silver salt and / or a halide.

The sensitizing dye is dissolved in a water-compatible organic solvent such as methanol, ethanol, propanol, fluorinated alcohol, methyl cellosolve, dimethylformamide, or acetone or water (which may be alkaline or acidic) and added. Or two or more of the above may be used in combination. It may also be added in the form of a dispersion in a water / gelatin dispersion or in the form of a lyophilized powder. Further, it may be added in the form of a powder or a solution dispersed using a surfactant.

The sensitizing dye used in the emulsion of the present invention may be, for example, those described in JP-A-3-296745 and JP-A-4-31854.

The amount of the sensitizing dye to be used is suitably from 0.001 g to 20 g, preferably from 0.01 to 2 g, per 100 g of silver used for emulsion production.

(Chemical Sensitization) The silver halide emulsion used in the present invention can be used as it is without chemical sensitization, but it is preferable to use a chemical sensitized emulsion having increased sensitivity. The chemical sensitization may be sulfur sensitization, gold sensitization, reduction sensitization, or any combination thereof.

In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur, such as selenium or tellurium, or chemical sensitization with a noble metal such as palladium or iridium may be combined with the above chemical sensitization.

Furthermore, 4-hydroxy-6-methyl-
A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound represented by (1,3,3a, 7) -tetraazaindene is also preferably used. The preferred range of the addition amount is 1
It is 10 ^-1 to 10 ^-5 mol per mol.

The pH at the time of chemical sensitization is preferably from 5.3 to
10.5, more preferably 5.5 to 9.5.

The sulfur sensitizer is a compound containing sulfur which can react with active gelatin or silver, for example, thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid ,
Rhodan, mercapto compounds and the like are used. In addition, U.S. Pat. Nos. 1,574,944 and 2,410,689.
No. 2,278,947, No. 2,728,668, and No. 3,656,955 can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ^{2 to} 10 g / m ² in terms of silver.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, selenium sensitization method, or the like can be used alone or in combination for an emulsion for a conventional light-sensitive material. These chemical sensitizations can also 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.

When the present invention is applied to a photothermographic material, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

The organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include US Pat.
Benzotriazoles, fatty acids and other compounds described in No. 26, columns 52-53 and the like. Japanese Patent Application Laid-Open No. 60-1
A silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate described in JP-A-13235;
The acetylene silver described in No. 249044 is also useful. Two or more organic silver salts may be used in combination.

The above-mentioned organic silver salts can be used as photosensitive silver halide 1
0.01 to 10 mol, preferably 0.1 to 10 mol, per mol.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

As the binder for the constituent layers of the light-sensitive material and the dye-fixing element, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are mentioned. 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, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more kinds.

In the case where a system for performing thermal development by supplying a small amount of water is used, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and 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 , particularly preferably 10 g or less, and more preferably 7 g or less.

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

As the reducing agent used in the present invention, those known in the field of photosensitive 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.

Examples of the reducing agent used in the present invention include:
U.S. Pat. Nos. 4,500,626, columns 49-50, 4,483,914, columns 30-31, 4,33.
0,617, 4,590,152, JP-A-60-1985.
140335, pages (17) to (18), 57-4
No. 0245, No. 56-138736, No. 59-178
No. 458, No. 59-53831, No. 59-18244
No. 9, No. 59-182450, No. 60-119555
Nos. 60-128436 to 60-128439
No. 60-198540, 60-18174
No. 2, 61-259253, 62-244444
No. 62-131256 to No. 62-131256
No. 78-9 of EP 220,746 A2.
There are reducing agents and reducing agent precursors described on page 6 and the like.

A combination of various reducing agents, such as those disclosed in US 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.

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). A particularly useful electron transfer agent is 1-phenyl-3.
-Pyrazolidones or aminophenols.

The non-diffusible reducing agent (electron donor) used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the photosensitive material among the above-mentioned reducing agents.
Preferred are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and JP-A-53-11.
Compounds described as electron donors in No. 0827 and dye-donating compounds having a diffusion-resistant and reducing property described later are exemplified.

In the present invention, the reducing agent is added in an amount of 0.01 to 20 mol, particularly preferably 0.1 to 1 mol per mol of silver.
10 to 10 mol.

In the present invention, when silver ions are reduced to silver under high-temperature conditions, a compound that generates or releases a mobile dye in response to this reaction or vice versa, that is, a dye donor An active compound.

Examples of the dye-donating compound other than the formula (I) which can be used in the present invention can be represented by the following general formula [LI]. (Dye-G) q-Y [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group (particularly one giving a magenta or cyan color), and q, G, and Y represent formulas It is synonymous with q, G, and Y in (II).

A hydrophobic additive such as a dye-donating compound or a nondiffusible reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, Japanese Patent Application Laid-Open No. 59-83154
Nos. 59-178451 and 59-178452
Nos. 59-178453 and 59-178454
A high-boiling organic solvent as described in JP-A Nos. 59-178455 and 59-178457 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C as necessary.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing compound 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-51-39853, JP-A-51-3985
A dispersion method using a polymer described in No. 59943 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.

In 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 capable of activating development and stabilizing an image at the same time as the light-sensitive material can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In the present invention, a non-diffusible filter dye can be contained for the purpose of improving sharpness and the like. If necessary, a filter dye having absorption in the infrared region can be used. For details of such a filter dye, see Japanese Patent Application No. 2-137885 and JP-A-4-217.
243, 4-276744, 5-45834 and the like.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive material. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. The relationship between the photosensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer described in US Pat. No. 4,500,626, column 57, can be applied to the present invention.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in US Pat. No. 4,500,626.
No. 58-59 and JP-A-61-88256 (3)
Mordants described on pages 2) to (41), JP-A-62-244;
Nos. 043 and 62-244036. No. 4,463,073.
A dye-receiving polymer compound as described in No. 9 may be used.

The dye-fixing element may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

As the binder for the constituent layers of the light-sensitive material and the dye-fixing element, hydrophilic binders are preferably used. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, a protein such as a gelatin derivative or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan, and polyvinyl alcohol;
Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Also, Japanese Patent Application Laid-Open
Superabsorbent polymers according to 245,260 No. etc., i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) copolymerizing the homopolymer or the vinyl monomer together or with other vinyl monomers of the vinyl monomer having a (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more kinds.

In the case of employing a system for performing thermal development by supplying a small amount of water, the use of the above superabsorbent polymer makes it possible to rapidly absorb water.
Further, when the superabsorbent polymer is used for the dye fixing layer and 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 1
It is preferably 20 g or less per m ² , particularly preferably 10 g or less, and more preferably 7 g or less.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. Specifically, Japanese Patent Application Laid-Open No. 62-253159 (2)
5), pages 62-245253 and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X).
-22-3710) are effective. In addition, JP
Silicone oils described in JP-A-2155953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794),
4-thiazolidone compounds (US Pat. No. 3,352,6)
No. 81), benzophenone-based compounds (JP-A-46-
2784, etc.), and JP-A-54-48535,
There are compounds described in JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As the metal complex, US Pat. No. 4,24
No. 1,155, No. 4,245,018, columns 3 to 36,
No. 4,254,195, columns 3-8, JP-A-62-1
Nos. 74741 and 61-88256 (27) to (2)
9), pp. 63-199248, JP-A-1-75556.
No. 8, No. 1-74272 and the like.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or supplied to the dye-fixing element from the outside such as a light-sensitive material. You may.

The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination.

A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., "The Chemis
try of 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 an anti-fading agent.

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

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, promoting development, and the like. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457.

The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the light-sensitive material and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952. The matting agent can be used for the purpose of making the surface (image surface) of the dye fixing element non-glossy in addition to the purpose of preventing adhesion, controlling slipperiness, and preventing Newton's ring.

In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the formation of a dye from a dye-providing substance or the decomposition of a dye or the release of a diffusible dye, and From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, and compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is described in U.S. Pat.
1,493, and JP-A-62-65038.

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, it is preferable to include a base and / or a base precursor in a dye-fixing element from the viewpoint of improving the storability of the light-sensitive material.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, a combination of a compound (hereinafter referred to as a complex-forming compound) capable of forming a complex with a metal ion constituting the hardly-soluble metal compound, Compounds that generate a base by electrolysis described in JP-A-61-232451 can also be used as the base precursor. In particular, the former method is effective. This poorly soluble metal compound and complex forming compound
It is advantageous to add them separately to the light-sensitive material and the dye-fixing element.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development.

The term "development terminator" used herein means that after appropriate development,
It is a compound that quickly neutralizes a base or reacts with a base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253159.
Nos. (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 a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used.

These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductor metal oxide such as alumina sol or tin oxide,
Carbon black or another antistatic agent may be applied.

As a method of exposing and recording an image on a light-sensitive material, image information is transmitted through an electric signal to a light emitting diode,
There are a method of performing exposure by emitting various lasers and the like, and a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system. Specifically, JP-A-2-129625, Japanese Patent Application Nos. 3-338182, 4-009388, and 4-
The exposure method described in JP-A-281442 can be used.

As a light source for recording an image on a photosensitive material,
As mentioned above, light emitting diode, laser light source, CRT
Light sources such as those described in U.S. Pat. No. 4,500,626, column 56, such as light sources, can be used.

[0224]

The present invention will be described in more detail with reference to the following examples.

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

Example 1 (Heat Developing Color Diffusion Transfer Method) A dye image-receiving element was prepared as follows. Poly (methyl acrylate-co-N, N, N-trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate to vinylbenzylammonium chloride is 1:
1) 10 g was dissolved in 175 ml of water and uniformly mixed with 100 g of 10% lime-processed gelatin. Add 2,4 to this mixture
25 ml of a 4% aqueous solution of -dichloro-6-hydroxy-1,3,5-triazine was added, and the mixture was uniformly coated on a paper support laminated with polyethylene in which titanium dioxide was dispersed to a thickness of 90 μm. Further, a 30 μm wet film thickness of a solution prepared by mixing and dissolving 6 g of guanidine picolinate, 18 ml of water, 20 g of 10% gelatin, and 4.8 ml of a 1% aqueous solution of 2-ethyl-hexyl ester succinate sodium sulfonate was applied. After drying, it is used as a dye fixing material K-1 having a mordant layer. The method of preparing the silver halide emulsion (I) of the third layer and the first layer will be described. 600 ml of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C.)
And an aqueous solution of silver nitrate (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously added at an equal flow rate over 40 minutes. Thus, an average particle size of 0.40 μm
Was prepared (50 mol% of bromine). After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, followed by chemical sensitization at 60 ° C.
The yield of the emulsion was 600 g.

Next, a silver halide emulsion for the fifth layer (II)
State how to make. A well-stirred aqueous gelatin solution (20 g gelatin and sodium chloride 3 in 1000 ml water)
g of sodium chloride and potassium bromide) and an aqueous solution containing sodium chloride and potassium bromide (600 ml) and silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 ml of water) at the same time over 40 minutes. Was added. Thus, a monodispersed cubic silver chlorobromide emulsion (80 mol% of bromine) having an average grain size of 0.35 μm was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 2
After 0 mg was added, chemical sensitization was performed at 60 ° C. The yield of the emulsion was 600 g.

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described. 12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethylcellulose as a dispersant, and 0.1% of sodium polyacrylate were added to 100 cc of a 4% aqueous gelatin solution, and milled to obtain an average particle size of 0.15 g.
Milled for 30 minutes using 75 mm glass beads. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. The oil phase components shown in the following Table-R were each dissolved in 50 cc of ethyl acetate to form a uniform solution at 60 ° C. To this, an aqueous phase component heated to 60 ° C. was added, and a disperser having a diameter of 8 cm with a dissolver having a diameter of 500 cm was used for 500 minutes.
Dispersed at 0 rpm. Post-water was added thereto and stirred to obtain a uniform dispersion. This is called a gelatin dispersion of the hydrophobic additive.

[0237]

[Table 1]

[0238]

Embedded image

Thus, a heat-developable color photosensitive element 401 having a multilayer structure shown in Table-S was produced.

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[Table 2]

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[Table 3]

[0242]

[Table 4]

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[0244]

Embedded image

[0245]

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[0246]

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The above photosensitive element 401 was exposed to laser under the conditions shown in Table-T. Next, the exposed photosensitive element was immersed in water maintained at 40 ° C. for 4 seconds, squeezed with a roller, and immediately superposed such that the image receiving element K-1 was in contact with the film surface.

[0248]

[Table 5]

Next, using a heat drum whose temperature was adjusted so that the temperature of the film surface having absorbed water became 80 ° C., heating was performed for 15 seconds, and the photosensitive element was peeled off from the image receiving element. A full-color image was obtained.
Next, the full-color image obtained as described above is
During irradiation with Xe light (17000 lux)
The light stability was investigated. Indicates a status A reflection density of 1.0
Measure the status A reflection density after irradiation of the part and before irradiation
Is stable at the residual ratio (percentage) with respect to the reflection density of 1.0
The light fastness was evaluated by evaluating the degree. As a result, it was found that the image derived from the dye of the present invention has extremely excellent light fastness.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/38 G03C 8/40 503 G03C 8/10 501

Claims (1)

(57) [Claims] 1. A silver halide photosensitive material comprising a support and a layer containing a dye-donating compound represented by the following general formula (II). General formula (II) (Dye- _Gq ) -Y In the formula (II), G represents a mere bond or linking group which is cleaved corresponding to or opposite to development, and Y represents an image-like latent image. Dye is released corresponding to the photosensitive silver halide or inversely corresponding thereto, and the released dye and (Dye-G) _q −
Represents a group having such a property as to cause a difference in diffusibility with the compound represented by Y, and q is 1 or 2, and when q is 2, two Dye-Gs are the same or different. You may. Dye is a dye residue of pyrazolopyrimidine-7 On'azo dye residue represented by the following general formula (I) (where formula (I), the metal ion complexes
Does not change ). Embedded image In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl, aryl, heterocyclic, cyano, alkoxy, aryloxy, acylamino, carbamoyl, acyl, alkoxycarbonyl Group, aryloxycarbonyl group, aminocarbonyl group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group, silyloxy group, heteryloxy group, alkylthio group, arylthio Group, heterylthio group, carboxylic acid group and sulfonic acid group. These groups may further have a substituent. A
r represents an aryl group or a heteroaromatic group derived from a diazo component, which may be substituted. However, Ar is
When the azo group has a substituent at the ortho position, the substituent is
It is not —OH or its hydrolyzable precursor group. R ² and R ³ may combine with each other to form a ring structure.
Dye and G are bonded at R ¹ , R ² , R ³ or Ar of the formula (I).