JP2001281827A - Color diffusion transfer photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color diffusion transfer photographic sensitive material having a short image appearance time, giving satisfactory maximum density and less liable to a density change in storage. SOLUTION: The color diffusion transfer photosensitive material has a non- diffusible dye image forming compound which forms or releases a diffusible dye or its precursor in connection with silver development or a dye image forming compound whose diffusibility varies in connection with silver development on the base, contains (a) a hydrazine type nucleus forming agent and (b) a compound selected from quinone derivatives capable of oxidizing the nucleus forming agent and having a specified structure and compounds of the formula AN=NB (where A and B are each a benzene or naphthalene ring) cleavable by electron acceptance in a constituent layer and has a color mixture preventing layer formed by coating with a dispersion of a non-diffusible reducing agent having <=0.2 μm average particle size between photosensitive silver halide emulsion layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color diffusion transfer photosensitive material. More specifically, the present invention relates to a color diffusion transfer photosensitive material which can form images quickly, provides a sufficient maximum density, and has a small density fluctuation during storage.

[0002]

2. Description of the Related Art In a color diffusion transfer photographic photosensitive material,
Obtain a direct positive image by developing the surface of an internal latent image type silver halide emulsion having a photosensitive nucleus mainly inside the silver halide emulsion and forming a latent image mainly inside the grain in the presence of a nucleating agent The method is widely known. It is effective to use a hydrazine-based compound as the nucleating agent used in this method. For example, US Pat. No. 4,341,858 and THJa
mes "The Theory of The Photographic Process" 4th edition (1977) Macmillan Publishing Co., Inc .. New
York and the like.

In the above method, a nucleating agent may be added to a developing solution. However, when the nucleating agent is added to the emulsion layer or other appropriate layer of the light-sensitive material, the nucleating agent is adsorbed on the surface of silver halide grains. , Better inversion characteristics can be obtained. For this purpose, a nucleating agent having a structure in which a hydrazine skeleton is used as a nucleation site and various adsorbing groups are bonded thereto is disclosed in, for example, US Pat. Nos. 4,080,207 and 4,278,748.
And British Patent 2,011,391B. An acylhydrazine-based nucleating agent having a mercapto group which gives a uniform and high maximum concentration is disclosed in JP-A-59-20.
0230. These nucleating agents are advantageous in that they can exhibit a nucleating action with a lower addition amount than compounds having no adsorptive groups.

However, even when these nucleating agents are used, in a photographic material in which the supply of oxygen to the silver halide emulsion layer is considered to be insufficient, the hydrazine compound has an insufficient nucleating effect. Image density cannot be obtained. As a technology to solve this problem, "Research Discl
osure ”Magazine No. 16929 (1978) and No. 1
6936 (1978), a method using a strong oxidizing agent such as ferricyanide in a silver halide emulsion layer, or a quinone oxidation method in a silver halide emulsion layer as described in the above-mentioned US Patent. Methods using agents have been proposed.

[0005] However, the above-mentioned method has a problem of insufficient maximum density and generation of stain, and the latter method has a problem of generation of stain in the lowest density portion. Therefore, give sufficient maximum density without generating stain,
Consequently, there has been a demand for an improved technique of using a nucleating agent to enable rapid image formation.

[0006] For this purpose, an example of adding a specific oxidizing agent to a silver halide emulsion layer is described in Japanese Patent Application No. 11-240602. When these oxidizing agents were added to the silver halide emulsion layer, it was found that a sufficient maximum density and rapid image formation can be obtained particularly in a color diffusion transfer photosensitive material using a hydrazine-based nucleating agent in combination.

However, when the above-described method is used, the density change during storage of the photosensitive material is large, and an improved technique has been desired.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color diffusion transfer photosensitive material and a color diffusion transfer film unit capable of forming an image quickly, giving a sufficient maximum density, and having a small density fluctuation during storage. It is to be.

[0009]

As a result of intensive studies, the present inventors have found that the objects of the present invention can be effectively achieved by the following photographic materials.

(1) A non-diffusible dye image-forming compound which forms or releases a diffusible dye or a precursor thereof in association with silver development on a support, or a dye image which is a compound which changes its diffusivity itself In a color diffusion transfer photosensitive material having at least two photosensitive silver halide emulsion layers combined with a forming compound, a hydrazine-based nucleating agent and a compound represented by any of formulas (I) to (III) capable of oxidizing the nucleating agent. A dispersion of a non-diffusible reducing agent containing at least one of the compounds represented by formula (1) and having an average grain size of 0.2 μm or less between the at least two photosensitive silver halide emulsion layers. A color diffusion transfer photosensitive material comprising a color mixture preventing layer.

[0011]

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In the formula (I), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. Substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group having 10 to 10 carbon atoms, substituted or unsubstituted aryl group, substituted or unsubstituted arylthio group, substituted or unsubstituted aryloxy group, halogen atom or cyano group Represents R ¹¹ and R ¹² or R ¹³ and R ¹⁴ may be linked to each other to form a ring.

[0013]

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In the formula (II), D ¹ and D ² may be the same or different and represent an atom group necessary for forming a benzene ring or a naphthalene ring. G ¹ and G ² may be the same or different and each represents a hydrogen atom or any substituent that does not adversely affect the photograph. A ¹ ,
A ² and A ³ may be the same or different and each represents a hydrogen atom or any substituent that does not adversely affect the photograph. B ¹ , B ² and B ³ may be the same or different and each represents a hydrogen atom or any substituent that does not adversely affect the photograph. L ¹ and L ² may be the same or different and represent a linking group, and m and n each represent 1 or 0. M ¹ and M ² may be the same or different from each other, and represent a component having a function of releasing an azo compound from the compound of the general formula (II) as a result of development, or a hydrogen atom.

[0015]

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In the formula (III), EAG represents an electron-accepting group. N and O represent a nitrogen atom and an oxygen atom, respectively. The nitrogen-oxygen atom is cleaved by the EAG receiving an electron from the reducing agent. R ³¹ and R ³² each represent a substituent other than a hydrogen atom that does not adversely affect the photograph. R
³¹ and R ³² , R ³¹ and EAG, and R ³² and EAG may combine with each other to form a ring.

(2) An image-receiving layer, a white reflective layer, a light-shielding layer, and a photosensitive silver halide emulsion layer combined with the dye image-forming compound on a transparent support, wherein the emulsion layer or at least one other layer is provided. A photosensitive sheet (A) containing the compound in a hydrophilic colloid layer, a transparent cover sheet (B) having at least a neutralization layer and a neutralization timing layer on a transparent support,
And a color diffusion film unit comprising a light-shielding alkali treatment composition (C) disposed so as to be spread between the photosensitive sheet (A) and the transparent cover sheet (B). The color diffusion transfer photosensitive material according to (1).

(3) An image receiving sheet (A) comprising at least a neutralizing layer, a neutralizing timing layer, an image receiving layer and a release layer on a support, and a dye-image-forming compound on a support provided with a light-shielding property. (B) a photosensitive sheet containing the compound, and the image-receiving sheet (A) and the photosensitive sheet containing the compound between the photosensitive silver halide emulsion layers or at least one of the other layers. The color diffusion transfer photosensitive material according to (1), which is a color diffusion transfer film unit composed of an alkali treatment composition (C) arranged so as to be developed between (B).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compound of the present invention will be described in detail.

First, the compound of the formula (I) will be described in detail. Examples of the substituent of the alkyl group or the alkyl residue of R11 to R14 include a hydroxy group and a sulfonamide group. Examples of the substituent of the aryl group or the aryl residue include an alkyl group having 1 to 5 carbon atoms. Further R11
And R12 or R13 and R14 are linked to form a 5- to 6-membered ring (for example, a benzene ring or the like, which may have an unsubstituted group such as an alkyl group). Specific examples of the compound of the general formula (I) are shown below.

[0021]

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[0022]

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[0023]

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Next, the general formula (II) will be described in detail.
In the general formula (II), G1, G2, A1, A2, A3, B1,
Examples of the substituents which do not adversely affect the photograph represented by B2 and B3 include halogen atoms, nitro groups, cyano groups, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups and -NHCOR31. (R31 represents an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, a substituted aralkyl group), -N
HSO2R31 (R31 is as defined above), -SOR31 (R31
Is as defined above), -SO2 R31 (R31 is as defined above),
-COR31 (R31 is as defined above), -CON (R32)
A group represented by (R33) (R32 and R33 may be the same or different and each represent a hydrogen atom, an alkyl group, a substituted alkyl group,
A phenyl group, a substituted phenyl group, an aralkyl group, or a substituted aralkyl group), -SO2N (R32) (R33) (R3
2, R33 has the same meaning as described above), an amino group (which may be substituted with an alkyl group), and a group which forms a hydroxyl group by hydrolysis.

Examples of the substituent of the above-mentioned substituted alkyl group, substituted alkoxy group, substituted phenyl group and substituted aralkyl group include an amino group, a hydroxyl group, a nitro group and a C 1 -C 1 group.
4, an alkoxy group represented by -NHSO2 R31 (R
31 is as defined above), and a group represented by -NHCOR31 (R31
Is as defined above), -SO2 (R32) (R33) (R32, R
33 is as defined above, a group represented by -CON (R32) (R33) (R32 and R33 are as defined above), -SO2 R31 (R31
Is as defined above), -COR31 (R31 is as defined above), a halogen atom, a cyano group, an amino group (which may be substituted with an alkyl group) and the like.

The linking group represented by L1 and L2 is preferably-[J1-K1- (J2-K2) p- (J3-K3) q
-] R-, and J1, J2 and J3 may be the same or different, and represent -CO-, -SO2-, -CON (R3
2)-(R32 is as defined above), -SO2N (R32)-
(R32 is as defined above), -N (R32) -CO- (R32 is as defined above), -N (R32) -SO2-(R32 is as defined above), -N (R32) -R34- (R32 Is as defined above, R
34 is an alkylene group having 1 to about 4 carbon atoms), -N (R32)-
R34-N (R33)-(R32, R33 and R34 are as defined above), -O-, -S-, -N (R32) -CO-N (R3
3)-(R32 and R33 are as defined above), -N (R32) -S
O2 -N (R33)-(R32 and R33 are as defined above).

K1, K2 and K3 may be the same or different and represent an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group or a substituted aralkylene group. Substitution of these substituted alkylene group, substituted arylene group and substituted aralkylene group can be selected, for example, from the listed atoms and groups. p, q
And r represent 0 or 1.

Among the compounds represented by the general formula (II), the following compounds are preferred. D1 and D2 may be the same or different and each represents an atom group necessary for forming a benzene ring or a naphthalene ring.

At least one of G 1 and G 2 represents an electron-withdrawing atom or group having a Hammett σ value greater than that of a fluorine atom, and specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, Examples thereof include an iodine atom, a nitro group, a cyano group, an alkylsulfonyl group, a sulfamoyl group, a sulfonamide group, and a carbamoyl group. For example,
J. Org. Chem., Vol. 23, 420
Page (1958). When only one of G1 and G2 is the above-mentioned electron-withdrawing atom or group, the other one is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, -SO2 R31 (R31 is -NHCOR31 (R31 is as defined above), -N
HSO2 R31 (R31 is as defined above), -CON (R32)
(R33) (R32 and R33 are as defined above), or -SO2N
(R32) and (R33) (R32 and R33 are as defined above).

A 1, A 2 and A 3 may be the same or different from each other and include a hydrogen atom, an alkyl group, a halogen atom,
A cyano group, -NHCOR31 (R31 is as defined above), -N
HSO2 R31 (R31 is as defined above), -SO2 R31 (R
31 is as defined above), -CON (R32) (R33) (R32,
R33 is as defined above), or -SO2 N (R32) (R33)
(R32 and R33 are as defined above).

B1, B2 and B3 may be the same or different from each other, but include a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, --SO2 R
31 (R31 is as defined above), -CON (R32) (R33)
(R32 and R33 are as defined above), or -SO2N (R32)
(R33) (R32 and R33 are as defined above). J is -C
O-, -SO2-, -CONH-, -SO2 NH-,-
Represents NHCO- or -NHSO2-.

K1, K2 and K3 may be the same or different and represent an alkylene group, an arylene group or a substituted arylene group. p, q and r represent 0 or 1.

Among the compounds of the general formula (II), those described below are particularly preferred. D1 represents an atomic group necessary for forming a benzene ring or a naphthalene ring, and D2 represents an atomic group necessary for forming a benzene ring.

At least one of G1 and G2 is a halogen atom (among others, a chlorine atom). When only one of G1 and G2 is a halogen atom, the other one is a hydrogen atom, an alkyl group or an alkoxy group. Represent. A1, A2 and A3 may be the same or different from each other and include a hydrogen atom, a halogen atom, an alkyl group, a cyano group, -NHCOR35 (R35 represents an alkyl group or a phenyl group), -NHSO2 R35
(R35 is as defined above), -SO2 N (R32) (R33)
(R32 and R33 are as defined above) or -CON (R32) (R
33) (R32 and R33 are as defined above).

B1, B2 and B3 may be the same or different from each other and include a hydrogen atom, a cyano group, a halogen atom,
Nitro group, alkyl group, -SO2 R35 (R35 is as defined above), -CON (R32) (R33) (R32 and R33 are as defined above), -SO2N (R32) (R33) (R32 and R33 are as defined above) Synonymous with).

J1 and J2 may be the same or different from each other, and include -CO-, -SO2-, -CONH-, -SO
2 represents NH-, -NHCO-, or -NHSO2-.
K1 and K2 may be the same or different and represent a phenylene group, a substituted phenylene group or an alkylene group. p and r represent 0 or 1, and q represents 0.

The nitro group substituted by the benzene ring completed by D1 or D2 is preferably located at the p-position or the o-position with respect to the azo group.

A preferred specific example when M1 and M2 are other than a hydrogen atom is a group represented by (ballast)-(redox cleavage atomic group)-. (Ballast)
-Is a group for substantially immobilizing the compound represented by the formula (II) in the photographic layer.

-(Redox cleavage group)-has a property of being cleaved by oxidation or reduction under thermal or alkaline conditions or a property of separating an azo compound portion bonded thereto by ring closure or the like. It is. Redox cleavage groups include US Patent No. 3,928,31.
No. 2, 3,993, 638, 4, 076, 529
Nos. 4,152,153 and 4,055,428
Nos. 4,053,312, 4,198,235
Nos. 4,179,291 and 4,149,892
No. 3,844,785, No. 3,443,943
Nos. 3,751,406 and 3,443,939
Nos. 3,443,940 and 3,628,952
Nos. 3,980,479 and 4,183,753
No. 4,142,891, No. 4,278,750
Nos. 4,139,379 and 4,218,368
No. 3,421,964, 4,199,355
No. 4,199,354 and 4,278,750
Nos. 4,135,929 and 4,336,322
No. 4,371,604, 4,139,389
Nos., JP-A-53-50736 and JP-A-52-4819,
No. 51-104343, No. 54-130122, No. 53-110827, No. 56-12624, No. 56
Nos. -16131, 57-4043 and 57-650
Nos. 57-20735, 53-69033, 54-130927, 56-164342, and 5
Those described in, for example, No. 7-119345 are effective.

A representative example of this group is an N-substituted sulfamoyl group. Specific examples of the compound represented by the general formula (II) include the following.

[0041]

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A11 = H II-2. In the formula II-1, A11 = Cl II-3. In the formula II-1, A11 = -NHCOCH3 II-4. In the formula II-1, A11 = -NHSO2CH3 II-5. In the formula II-1, A11 = CN II-6. In the formula II-1, A11 = -SO2N (iso
-C3H7) 2 II-7. In the formula II-1, A11 = -CON (C2H5) 2

[0043]

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II-9. In the formula II-8, K11 = -C16
H32-, M11 = H

[0045]

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[0046]

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[0047]

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However, B11 = H II-13. In the formula II-12, B11 = -NO2 II-14. In the formula II-12, B11 = -Cl II-15. In the formula II-12, B11 = -CN II-16. In the formula II-12, B11 = Br

[0049]

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[0050]

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Next, the general formula (III) will be described in detail. R31 and R32 may be the same or different and each represents a substituent other than hydrogen, and is preferably an alkyl group, an aryl group, a heterocycle, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfonyl group, an aryloxycarbonyl group or Represents a sulfamoyl group. These groups may be substituted by other groups.

Generally, the reduction potential can be increased by making the substituent of the oxygen atom or the nitrogen atom an electron-withdrawing group. The same tendency is observed for the substituent of the electron-accepting group, and the reduction potential (oxidizing power) increases as the electron-withdrawing property increases.

The compound represented by the general formula (III) can be used for the above-mentioned applications and furthermore as an oxidizing agent (for example, in order to increase the degree of freedom with respect to the reduction potential, the stability of the compound and the synthetic design, The compound represented by the general formula (IIIa) is preferable.

[0054]

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In the formula (IIIa), R33 represents an atomic group necessary for bonding to a nitrogen atom or an oxygen atom to form a 3- to 8-membered monocyclic or condensed heterocyclic ring. R33 may combine with EAG to form a ring.

The meanings of the other formulas are the same as those described in the general formula (III), and will be described in more detail below. E
AG represents a group that receives an electron from a reducing substance and is bonded to a nitrogen atom. As the EAG, a group represented by the general formula (A) or (B) described in the general formula (I) is preferable.

R33 represents an atomic group necessary for forming a 3- to 8-membered heterocyclic ring by bonding to a nitrogen atom and an oxygen atom, as described above. Some examples of this heterocyclic ring are shown below.

[0058]

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[0059]

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Here, R36, R37 and R38 may be the same or different and each is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfonyl group, an aryloxycarbonyl. Group,
Sulfamoyl group, cyano group, nitro group, halogen atom, amino group, alkoxy group, aryloxy group, hydroxyl group, ureido group, aminocarbonyloxy group,
Alkoxycarbonylamino group, amide group, sulfo group,
Represents a carboxy group, a sulfonamide group, an acyloxy group, or an aryloxycarbonylamino group.

Among the compounds represented by the general formula (IIIa), the compound represented by the general formula (IIIb) can be mentioned as an example showing more sufficient properties as an oxidizing compound.

[0062]

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The EAG is as described above.
X 'represents a divalent linking group, particularly preferably -C (=
O)-or -SO2-.

R34 and R35 each represent a hydrogen atom or a group capable of substituting a hydrogen atom, and may be bonded to each other to form a saturated or unsaturated carbocyclic or heterocyclic group.

Preferred examples of R34 and R35 include a hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a t-butyl group, an octadecyl group, a phenethyl group, a carboxymethyl group), a substituted or unsubstituted alkyl group. Substituted aryl groups (for example, phenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, 4-tetradecyloxyphenyl group Etc.), substituted or unsubstituted heterocyclic groups (eg, 2-pyridyl group, 2-furyl group, 3-pyridyl group, etc.), acyl groups (eg, acetyl group, benzoyl group, dodecanoyl group, 4-acetamidobenzoyl group) Etc.), alkoxycarbamoyl groups (for example, methoxycarbonyl group, methoxyethoxycarbonyl group , Butoxycarbonyl group),
Carbamoyl group (for example, carbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group, diethylcarbamoyl group, dodecylcarbamoyl group, etc.), sulfonyl group (for example, methanesulfonyl group, p-toluenesulfonyl group, hexadecylsulfonyl group, etc.), aryloxycarbonyl group (Eg, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, dimethylsulfamoyl group, butylsulfamoyl group, phenylsulfamoyl group, etc.),

A cyano group, a nitro group, a halogen atom (for example, F, Cl, Br, I, etc.), an amino group (for example, amino group, methylamino group, diethylamino group, methylphenylamino group, 1-pyrrolidino group, etc.), Alkoxy group (for example, methoxy group, ethoxy group, octyloxy group,
An isopropyloxy group, an aryloxy group (eg, a phenoxy group, a 4-chlorophenoxy group, a 3-pendadecylphenoxy group, etc.), a hydroxyl group, a ureido group (eg, a 3-methylureido group, a 3,3-diethylureido group, 1-methyl-3-phenylureido group), aminocarbonyloxy group (for example, dibutylaminocarbonyloxy group, phenylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, hexyloxy Carbonylamino group, amide group (eg, acetamide group, benzamide group, etc.), sulfo group or salt thereof, carboxyl group or salt thereof, sulfonamide group (eg, methanesulfonamide group, phenylsulfone Bromide group, and dodecyl sulfonamido group), an acyloxy group (such as acetoxy group, benzoyloxy group), an aryloxy carbonyl amino group (e.g., phenoxycarbonylamino group).

Examples of the case where R34 and R35 form a ring to form a condensed ring include the following.

[0068]

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Next, specific examples of the compound represented by the general formula (III) will be listed, but the scope of the present invention is not limited to these specific examples.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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The layer containing the compounds (I) to (III) is preferably a layer containing silver halide or a layer adjacent thereto. Especially, it is most preferable to add it to a silver halide emulsion layer.

The compounds (I) to (III) according to the present invention 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, any high-boiling solvent or low-boiling solvent can be used. The addition amount is suitably 0.05 to 5 mmol / m ² , and preferably 0.1 to 1 mmol / m ² .

Next, the color mixture preventing layer will be described in detail.
The non-diffusible reducing agent used in the color mixture prevention layer is preferably selected from non-diffusible hydroquinone derivatives, sulfonamidophenol derivatives, and sulfonamidonaphthol derivatives. Particularly, a non-diffusible hydroquinone derivative is preferable. Further, dialkyl hydroquinone derivatives are preferred. Here, the alkyl group includes a substituted or unsubstituted alkyl group, and the substituent is a “non-diffusible”
There is no particular limitation as long as it does not inhibit. Specific examples include an aryl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. The total carbon number of the “dialkyl group” is preferably 12 or more, more preferably 16 or more.

[0084]

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[0085]

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In the present invention, a water-insoluble and low-boiling organic solvent-soluble homopolymer having a repeating unit having a —C (＝ O) —O— bond in the main chain or side chain used together with the non-diffusible reducing agent is used. As a union or copolymer,
Homopolymers and copolymers described in Japanese Patent Application No. 0-18978 and polymers described in Japanese Patent Application No. 9-143891 can be used.

As specific compounds, polyvinyl acetate, polyvinyl propionate, vinyl acetate-vinyl alcohol copolymer (90:10), polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate , Polyisobutyl methacrylate, polyisopropyl methacrylate, polyoctyl acrylate, poly-t-butyl methacrylamide, butyl acrylate
Acrylamide copolymer (95: 5), stearyl methacrylate-acrylic acid copolymer (90:10), 1,
Examples include, but are not limited to, 4-butanediol-adipate polyester, ethylene glycol-sebacate polyester, polycaprolactone, polypropiolactone, polydimethylpropiolactone, and the like. These polymers can be used alone or in combination.

The low-boiling organic solvent used in the present invention can be used as long as it can dissolve the non-diffusible reducing agent and polymer used, and is usually used in emulsified dispersion. Specifically, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone and the like having a boiling point of less than about 140 ° C. can be used. These low-boiling organic solvents can be used alone or in combination.

The hydrophilic organic colloid in which the mixture of the non-diffusible reducing agent and the polymer is dispersed according to the present invention includes, for example, gelatin (acid-treated gelatin, alkali-treated gelatin, demineralized gelatin), allylating agent Such as gelatin derivatives (acylated gelatin, phthalated gelatin, etc.), gelatin grafted by vinyl polymers, proteins such as casein, albumin; hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose,
Cellulose derivatives such as; polyvinyl alcohol, polyacrylamide, polyvinyl ethers, polymer non-electrolyte such as polymethyl ether, polyacrylic acid,
An anionic synthetic polymer such as a partial hydrolyzate of polyacrylamide can be used. These hydrophilic organic colloids can be used alone or in combination.

In a desirable step of preparing a dispersion of individual particles in which the non-diffusible reducing agent and the polymer of the present invention are integrated, the non-diffusible reducing agent and the polymer are dissolved in a low boiling organic solvent. Then, an aqueous solution of a hydrophilic organic colloid is added thereto, and an emulsion is prepared using an emulsifying and dispersing machine such as a homogenizer. The dispersion is significantly aided by using a surfactant as an emulsifying aid. Useful surfactants are described, for example, in the above-mentioned patent specification and JP-B-39-4.
923, U.S. Pat. No. 3,676,141.

The above-mentioned dispersion in which the non-diffusible reducing agent and the polymer of the present invention are integrated with each other is emulsified and dispersed so that the content of the low-boiling organic solvent is 0.2 wt% or more and 4 wt% or less. It is necessary to remove low boiling organic solvents. In order to remove the low-boiling organic solvent, a method of removing the low-boiling organic solvent by heating and reducing the pressure of the emulsified dispersion, adding water to the emulsified dispersion and concentrating the mixture with an ultrafiltration membrane to obtain a water-soluble organic solvent. There are a method of removing the low-boiling organic solvent together with water, and a method of cooling and emulsifying the emulsified dispersion to form a so-called noodle so as to wash and remove it. Although any method can achieve the object of the present invention, the above-mentioned heating / decompression method and ultrafiltration method are preferable.

As a result of various studies, the present inventors have found that the average size of the emulsified dispersion particles in which the non-diffusible reducing agent and the polymer are integrated is 0.2 μm or less, and the content of the low boiling organic solvent is Diffusion transfer using a dispersion in which the weight ratio of the polymer to the hydrophilic organic colloid (solid content) in the dispersion is 0.2 to 1.5 wt% for the color mixture preventing layer. It has been found that an image having a high image density at a low temperature and excellent in color reproducibility can be quickly obtained by the photosensitive material, and the density fluctuation after completion of the image is small.

Further, as a result of diligent studies, the present inventor has found that when the oxidizing agent described above is used, the color diffusion transfer photosensitive material having the non-diffusible reducing agent emulsified and dispersed particles having an average particle size of 0.2 μm or less is used. The present inventors have also found that the concentration change during storage is significantly reduced depending on the material, and the present invention has been achieved. The average particle size of the emulsified and dispersed particles is 0.05 to 0.1.
2 μm is preferred, and 0.1 to 0.2 μm is more preferred.

Next, the color diffusion transfer photosensitive material of the present invention will be described. In a typical form of the color diffusion transfer film unit, the image receiving element and the photosensitive element are laminated on one transparent support, and after the transfer image is completed, there is no need to peel the photosensitive element from the image receiving element. It is a form. More specifically, the image receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a blue-sensitive emulsion layer, a combination of a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer, A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound, magenta The dye image-forming compound and the cyan dye image-forming compound are respectively combined (herein, the term “infrared-sensitive emulsion layer” means 700 nm or more, especially 74 nm).
An emulsion layer having a spectral sensitivity maximum with respect to light of 0 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example,
67840 and Canadian Patent 674,082.

As another embodiment of a laminate type, which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, a white support described in JP-A-63-226649. (C) a release layer, (d) a photosensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming compound, an alkali treatment composition containing a light-shielding agent, and a transparent cover sheet, the emulsion layer comprising There is a color diffusion transfer photographic film unit having a layer having a light-shielding function on the side opposite to the side where the processing composition is spread.

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

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type, and the other is of a peeling-free type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image-receiving layer is coated on one support, and the photosensitive element is coated on a support having a light-shielding layer. Before the end of the exposure, the coated surface of the photosensitive layer and the coated surface of the mordant layer do not face each other, but after the end of the exposure (for example, during the developing process), the coated surface of the photosensitive layer is inverted in the image forming apparatus and is in contact with the coated surface of the image receiving layer. It is devised as follows. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

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

A pressure-rupturable container (processing element) further containing an alkaline processing liquid may be combined with the above-described embodiment. In particular, in a non-peelable film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet superposed thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains one or both of a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, it is preferable that a neutralization timing mechanism composed of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element. Hereinafter, each component that can be used in the light-sensitive material of the present invention will be described in more detail.

I. Photosensitive Sheet A) Support The support of the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic photosensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. The thickness of the support is 5
It is 0 to 350 μm, preferably 70 to 210 μm, and more preferably 80 to 150 μm. If necessary, a layer for curl balance or an oxygen barrier layer described in JP-A-56-78833 may be provided on the back side of the support.

B) Image Receiving Layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer containing a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Things. The coating amount of the mordant is generally 0.5
10 to 10 g / m2, preferably 1.0 to 5.0 g / m2, particularly preferably 2 to 4 g / m2.

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred. In the image receiving layer, JP-A-62-30620
No. 62-30621, JP-A-62-215272.
The anti-fading agent described in (1) can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. As white pigments for the white reflective layer, barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. These may be used alone or as a mixture as long as the desired reflectance is obtained. A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of the pigment, the mixing ratio of the pigment and the binder, and the amount of the pigment applied. It is desirable that the light reflectance is 70% or more. In general, as the amount of the pigment applied increases, the whiteness improves.However, when the image forming dye diffuses through this layer, the pigment becomes resistant to the diffusion of the dye. Is desirable. 5 to 40 g / m2 of titanium dioxide
Preferably, the white reflective layer is coated at 10 to 25 g / m 2 and has a light reflectance of 78 to 85% with light having a wavelength of 540 nm. Titanium dioxide can be selected from various commercially available brands. Among them, it is particularly preferable to use rutile type titanium dioxide. Many commercial products are
Surface treatment is performed with alumina, silica, zinc oxide, or the like, and a surface treatment amount of 5% or more is desirable in order to obtain high reflectance. Commercially available titanium dioxide includes, for example, those described in Research Disclosure No. 15162 in addition to Ti-pure R931 manufactured by DuPont.

As a binder for the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be used. A particularly desirable binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1/1 to 2
0/1 (weight ratio), preferably 5/1 to 10/1 (weight ratio). In the white reflective layer, JP-B-62-3062
It is preferable to incorporate an anti-fading agent such as No. 0 or No. 62-30621.

D) Light-Shielding Layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used. U.S. Pat.
Degradable dyes described in US Pat. No. 5,966 or the like may be used.
As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred. As a carbon black raw material, for example, D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any production method such as a channel method, a thermal method and a furnace method described in 976) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 °. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shielded from light, but is preferably about 5 to 10 in optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming compound is provided above the light-shielding layer. The components will be described below.

(1) Dye image forming compound Specific examples of the dye image forming compound are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,453
No. 107, No. 3,544,545, No. 3,932,3
No. 80, No. 3,931,144, No. 3,932,30
No. 8, 3,954, 476, 4, 233, 237
Nos. 4,255,509 and 4,250,246
Nos. 4,142,891, 4,207,104
No. 4,287,292, JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36804,
No. 56-73057, No. 56-71060, No. 55
-134, JP-A-7-120901 and 8-286
No. 343, No. 8-286344, No. 8-292535
What is described in the issue.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827.
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17,630 (1978) and 16,475 (1977).

A dye image-forming compound which forms a dye by coupling can also be used. For example, JP-A-8-28634
No. 0, No. 9-152705, Japanese Patent Application No. 8-357190
And Nos. 8-357191 and 9-117529. Also, a positive dye image forming compound can be used. In this case, a negative emulsion may be used as the silver halide emulsion. An example of this is disclosed in Japanese Patent Laid-Open No. 4-156542.
Nos. 4-155332, 4-172344, 4-172450, 4-318844, and 356
046, 5-45824, 5-45825,
5-53279, 5-107710, 5-2
No. 41302, No. 5-107708, No. 5-2326
No. 59, U.S. Pat. No. 5,192,649.

These compounds are disclosed in JP-A-62-2152.
No. 72, pages 144 to 146. These dispersions are described in JP-A-62-2152.
No. 72, pages 137 to 144 may be included. Specific examples of these dye-forming compounds include the following compounds. Dye in the following compounds represents a dye group, a temporarily shortened dye group, or a dye precursor group.

[0114]

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[0115]

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[0116]

Embedded image

(2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion which forms a latent image mainly on the surface of silver halide grains, or a latent image which is formed inside silver halide grains. An internal latent image type direct positive emulsion to be formed may be used.

The internal latent image type direct positive emulsion may be, for example, a so-called “conversion type” emulsion prepared by utilizing the difference in solubility of silver halide, or may be doped with a metal ion.
Or a "core / shell" emulsion in which at least the photosensitive sites of the silver halide inner nucleus (core) grains subjected to chemical sensitization or both are coated with an outer shell of silver halide. These are described in U.S. Pat. Nos. 2,592,250 and 3,206,313, British Patent 1,027,146, and U.S. Pat.
Nos. 6, 3,935,014 and 3,447,927
No. 2,297,875, No. 2,563,785
Nos. 3,551,662 and 4,395,478
No. 2,728,108, US Patent 4,43.
1,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to give a surface fog nucleus using light or a nucleating agent after image exposure. As a nucleating agent for that,
U.S. Pat. Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat. No. 3,227,5
No. 52, hydrazines and hydrazones described in British Patent No. 1,283,835, JP-A-52-69613.
No. 3,615,615 and 3,719,4
Nos. 94, 3,734, 738 and 4,094,68
Heterocycle 4 described in No. 3, No. 4, 115, 122, etc.
Grade salt compounds, sensitizing dyes having a nucleating substituent described in US Pat. No. 3,718,470 in dye molecules, US Pat. Nos. 4,030,925 and 4,031,1
No. 27, No. 4, 245, 037, No. 4, 255, 51
No. 1, 4,266,013, 4,276,364
Thiourea-linked acylhydrazine-based compounds described in US Pat. No. 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748, British Patent 2,011,391B and the like An acylhydrazine-based compound in which a heterocyclic group such as a thioamide ring or a triazole or a tetrazole described in (1) is bonded as an adsorptive group is used.

In the present invention, spectral sensitizing dyes can be used in combination with these negative emulsions and internal latent image type direct positive emulsions. For a specific example thereof, see JP-A-59-18.
Nos. 0550 and 60-140335, Research Disclosure (RD) 17029, U.S. Pat.
No. 6,300, No. 2,078,233, No. 2,08
9,129, 2,165,338, 2,23
No. 1,658, No. 2,917,516, No. 3,35
No. 2,857, No. 3,411,916, No. 2,29
5,276, 2,481,698, 2,68
8,545, 2,921,067, 3,28
2,933, 3,397,060, 3,66
No. 103, No. 3,335,010, No. 3,35
2,680, 3,384,486, 3,62
No. 3,881, No. 3,718,470, No. 4,02
5,349 and the like.

(3) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the above-mentioned dye which provides a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above-mentioned spectral sensitizing dye is used. A photosensitive layer comprising at least two of the combination with the image forming compound is used. The emulsion and the dye image-forming compound may be coated as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming compound layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, a partition layer described in JP-B-60-15267 is provided to increase the color image density, or a reflective layer is provided to provide a photosensitive layer. It can also increase the sensitivity of the element.

The reflection layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide is 0.1 g / m2 to 8 g / m2, preferably 0.2 g / m2 to 4 g / m2. Examples of the reflective layer are described in JP-A-60-91354.

In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side. Arbitrary layers can be provided between the emulsion layer units as needed.
In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer, and the like are provided as needed.

F) Release Layer In the present invention, a release layer can be provided, if necessary, for peeling off the photosensitive sheet in the unit at an arbitrary place after processing. Therefore, this release layer must be easily peelable after the treatment.

Materials for this purpose include, for example,
Nos. 7-8237, 59-220727 and 59-2
No. 29555, No. 49-4653, U.S. Pat.
20,835 and 4,359,518,
No.-4334, No.56-65133, No.45-240
No. 75, U.S. Pat. Nos. 3,227,550 and 2,75
9,825, 4,401,746, 4,36
No. 6,227 or the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like.
Other examples include various natural polymers such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Further, another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate,
Polybutyl methacrylate or a copolymer thereof. The release layer can be a single layer or, for example,
It may be composed of a plurality of layers as described in JP-A-59-220727 and JP-A-60-60642.

The color diffusion transfer photosensitive material of the present invention preferably has a neutralizing function between the support and the photosensitive layer, between the support and the image receiving layer, or on the cover sheet.

G) Support The support for the cover sheet used in the present invention may be any smooth transparent support commonly used for photographic light-sensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. ,
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of a dye to prevent light piping.

H) Layer Having a Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali introduced from the treatment composition. Accordingly, a multilayer structure including layers such as a neutralization rate control layer (timing layer) and an adhesion strengthening layer may be used. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that provides such an acidic group by hydrolysis), and more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. Ester copolymers;
No. 4,139,383 and Research Disclosure No. 16102 (19
And latex-type acidic polymers as disclosed in (77). In addition, U.S. Pat.
8,493, JP-A-52-153739, and JP-A-53-153739.
No. 1023, No. 53-4540, No. 53-4541
And the acidic substances disclosed in JP-A-53-4542 and the like.

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiene phthalate and the like.

The above-mentioned polymer acids can be used as a mixture with a hydrophilic polymer. Such polymers include:
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer in the polymer acid,
For example, cellulose acetate or the like may be mixed.

The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is from 0.1 to 10, preferably from 0.1 to 10.
3 to 3.0.

In the layer having a neutralizing function of the present invention, additives can be incorporated for various purposes. For example, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. Other, if necessary,
An antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof can also be added.

The timing layer used in combination with the neutralizing layer has a low alkali permeability such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like. Polymers made by copolymerizing small amounts of hydrophilic comonomers such as acrylic acid monomers,
Latex polymers that increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

Among them, JP-A-54-136328,
U.S. Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849 and the like, a timing layer using cellulose acetate;
No. 335, No. 56-69629, No. 57-6843
No. 4,056,394 and 4,061,4
Nos. 96, 4,199,362, 4,250,24
No. 3, 4,256, 827, 4,268,604
A latex polymer prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; a polymer having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346 and 57-6842, European Patent (EP) 31,957A1, 37,72
The polymers disclosed in Nos. 4A1, 48,412 A1, and the like are particularly useful.

In addition, those described in the following documents can also be used. U.S. Pat. Nos. 3,421,893 and 3,455
686, 3,575,701, 3,778,2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, 4,088, 493, 4, 123, 275
No. 4,148,653, 4,201,587
No. 4,288,523 and 4,297,431
No., West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disclosure 1516
2, No. 151 (1976). The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

In addition, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) No. 2,913,164, and US Pat.
No. 72, JP-A Nos. 54-155837 and 55-138.
No. 745, and the like, and a development inhibitor and / or a precursor thereof disclosed in US Pat.
Hydroquinone precursor disclosed in No. 78,
It is also possible to incorporate other useful photographic additives or precursors thereof. Further, as a layer having a neutralization function, JP-A-63-168648 and JP-A-63-168648
Providing an auxiliary neutralizing layer as described in JP-B-168649 is effective in that a change in transfer density with time after processing is reduced.

I) Others In addition to the layer having a neutralizing function, a layer having an auxiliary function may have a back layer, a protective layer, a filter dye layer and the like. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used for preventing adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are overlapped. The sensitivity of the photosensitive layer can be adjusted by adding a dye to the cover sheet. The filter dye is directly in the support of the cover sheet or a layer having a neutralizing function, and further the back layer,
You may add to a protective layer, a capture mordant layer, etc., and may provide a single layer.

II. Alkali processing composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is disposed on the back of the support or on the side opposite to the processing solution of the photosensitive layer to form a pair with the light shielding layer. Thus, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the contained components. For this purpose, the composition contains an alkali, a thickener, a light-blocking agent, a developer, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developer. Etc. A light-shielding agent is always contained in the composition for light-shielding.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes a hydroxide of an alkali metal (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickener is used in order to spread the treatment liquid uniformly.
Also, it is necessary to maintain the close contact between the photosensitive layer and the cover sheet. For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used. As the light-shielding agent, any dye or pigment can be used as long as the light-shielding agent does not diffuse to the dye image-receiving layer to produce stain, or a combination thereof. A typical example is carbon black.

As the preferred developing agent, any one can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially generate stain even when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and the like.

Either a photosensitive sheet, a cover sheet or an alkali treatment composition, a development accelerator described in JP-A-62-215272, pages 72 to 91, a hardener described in pages 146 to 155, a hardener described in pages 201 to 210 Surfactant, 210
Fluorine-containing compounds described on pages 223 to 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 23
It may contain a polymer latex described on pages 0 to 239, a matting agent described on page 240, and the like. Also, Japanese Patent Laid-Open No. 6-2
73907, JP-A-7-134386, JP-A-7-134386
No. 175193 and JP-A-7-287372.
A graded amine latex can be included.

These alkaline liquid compositions have a developed thickness (amount of the processing liquid per m 2 after transferring the processing liquid) of 20 μm to 2 μm.
It is desirable that the image is spread on the photosensitive element at a thickness of 00 μm. The processing temperature when processing the photographic material is preferably from 0 to 50C, more preferably from 0 to 40C.

The details of the heat-developable color light-sensitive material (dye-fixing element) in which the dye image-forming compound of the present invention is used, and the exposure / heating method and apparatus to be applied are described in, for example, JP-A-7-219180, [0128] From [01
59].

[0145]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 First, a method for preparing a silver halide emulsion will be described. The following eight kinds of silver halide emulsion grains (emulsion-A to emulsion-F) and emulsion-T,
U was prepared.

Preparation of Emulsion-A (octahedral internal latent image type direct positive emulsion): 0.05 M potassium bromide, 1 g 3,6-dithia-1,8-octanediol, 0.034 mg lead acetate
And deionized gelatin 60 having a Ca content of 100 ppm or less
g in 1000 ml of an aqueous gelatin solution containing
While maintaining the temperature at 5 ° C., a 0.4 M aqueous solution of silver nitrate and a 0.4 M aqueous solution of potassium bromide were controlled by the double jet method while controlling the addition rate of the aqueous solution of potassium bromide so that the pBr was 1.60. Was added over 40 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having an average particle size (equivalent sphere size) of about 0.7 μm and a uniform particle size were produced.

Next, core chemical sensitization was performed under the following conditions. 1. Tank: Hemispherical bottom with a 120 μm thick Teflon-coated metal surface made of a fluororesin FEP developed by Du Pont. 2. Stirring impeller: Seamless, integral type propeller type with a metal surface coated with Teflon (registered trademark).

Sodium thiosulfate 1 was added to the preparation of Emulsion-A.
mg, potassium tetrachloroaurate 90 mg and potassium bromide 1.
3 g of an aqueous solution of 2 g dissolved in 1000 ml of water is added,
Chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes. 0.1% was added to the emulsion solution thus chemically sensitized.
After the addition of 5 M potassium bromide, a 0.9 M aqueous solution of silver nitrate and a 0.9 M aqueous solution of potassium bromide are added to the aqueous solution of 0.9 M potassium bromide in a controlled double jet method while maintaining the temperature at 75 ° C., as in the preparation of the core particles. The silver nitrate aqueous solution 6
70 ml was added over 70 minutes. The emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to make the average particle size (equivalent sphere size) about 1.2 μm. Octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained.

Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to the internal latent image type core / shell emulsion.
Was added to 1000 ml of water and 3 ml of an aqueous solution was added.
After addition of mg of poly (N-vinylpyrrolidone) and aging at 60 ° C., 0.005 M potassium bromide was added to prepare an octahedral internal latent image type direct positive emulsion.

Preparation of emulsions BF (octahedral internal latent image type direct positive emulsion): In the preparation method of emulsion-A, the addition time of silver nitrate aqueous solution and potassium bromide aqueous solution was changed, and the amount of added chemicals was further changed. Was carried out to obtain an octahedral internal latent image type direct positive silver halide emulsion having an average particle size (equivalent sphere diameter) shown in Table 1 having a uniform particle size.

[0152]

[Table 1]

Preparation of Emulsion-T (hexagonal tabular internal latent image type direct positive emulsion): In 1.2 liter of an aqueous gelatin solution containing 0.05 M potassium bromide and 0.7% by weight of gelatin having an average molecular weight of 100,000 or less. And 1.4 containing the aforementioned gelatin.
33 ml of each of the M aqueous silver nitrate solution and the 2 M aqueous potassium bromide solution were simultaneously mixed for 1 minute by the double jet method with vigorous stirring. During this time, the gelatin aqueous solution was kept at 30 ° C. Further, 300 ml of a gelatin solution containing 10% by weight of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 40 ml of 0.9 M silver nitrate aqueous solution
Was added over 3 minutes, and a 25% by weight aqueous ammonia solution was added, followed by aging at 75 ° C. After the ripening, ammonia was neutralized, and then 5 mg of lead acetate (added as an aqueous solution) was added, and an accelerated flow rate of 1 M silver nitrate aqueous solution and 1 M potassium bromide aqueous solution while maintaining pBr at 2.5 (at the end of the aging) (The flow rate was 6 times the flow rate at the start) and added by the double jet method (the amount of the used silver nitrate aqueous solution was 500 ml).

The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto, and 750 g of a hexagonal flat plate was added. Core particles were obtained. The obtained hexagonal flat core particles have an average projected area circle equivalent diameter of 0.9 μm and an average thickness of 0.20.
μm, and 95% of the total projected area was occupied by hexagonal tabular grains.

Next, core chemical sensitization was performed under the following conditions. 1. Tank: Fluororesin material F developed by DuPont for metal surface
Hemisphere bottom shape with Teflon coating with thickness of 120μm by EP. 2. Stirring impeller: Seamless, integral type propeller type with metal surface coated with Teflon.

200 g of the above hexagonal tabular core emulsion was mixed with water 13
00ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C, 3,6-dithia-
2.4 g of an aqueous solution obtained by dissolving 0.3 g of 1,8-octanediol, 10 mg of sodium benzenethiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) And heated at 75 ° C. for 180 minutes to perform a chemical sensitization treatment. In the same manner as in the preparation of the core particles, the chemically sensitized core particles were mixed with a 2M aqueous solution of silver nitrate.
The double jet method was carried out at an accelerated flow rate (the flow rate at the end was 3 times the flow rate at the start) while adjusting the addition rate of the aqueous solution of potassium bromide to adjust the pBr to 2.2. (The amount of the used aqueous silver nitrate solution was 810 ml).

After adding 0.3 M potassium bromide, the emulsion was washed with water by a conventional flocculation method, and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains have an average projected area circle equivalent diameter of 2.0 μm, an average thickness of 0.38 μm, an average volume size of 1.3 (μm) 3, and 88% of the total projected area are hexagonal tabular grains. Occupied by particles. Next, 100 mg of sodium thiosulfate and 4 parts of sodium tetraborate were added to the hexagonal tabular internal latent image type core / shell emulsion.
15 mg of an aqueous solution in which 0 mg was dissolved in 1000 ml of water was added, and 20 mg of poly (N-vinylpyrrolidone) was further added.
By heating at 100 ° C. for 100 minutes, the grain surface was chemically sensitized to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-U (hexagonal tabular internal latent image type direct positive emulsion): When forming the outer shell of Emulsion-T, 0.15 mol% of iodine was uniformly contained, and the outer shell forming amount was further reduced. By increasing, the average projected area circle equivalent diameter becomes 2.5
The average grain size was 0.45 μm, the average volume size was 1.7 (μm) 3, and 88% of the total projected area was occupied by hexagonal tabular grains. Next, AgI corresponding to 0.04 mol% of the silver amount required for grain formation at the start of shell chemical sensitization of the hexagonal tabular internal latent image type core / shell emulsion was used.
After adding the fine grain emulsion-X, the same shell chemical sensitization as in the emulsion-T was performed to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-X (AgI fine grain emulsion) 0.5 g of potassium iodide and 26 g of gelatin were added to water, and 80 g of an aqueous silver nitrate solution containing 40 g of silver nitrate and 39 g of iodine were stirred into a solution kept at 35 ° C. while stirring. 80 cc of an aqueous solution containing potassium iodide was added over 5 minutes. At this time, the addition flow rates of the silver nitrate aqueous solution and the potassium iodide aqueous solution were each 8 ml / min at the start of the addition, and the addition flow rates were linearly accelerated so that the addition of 80 ml was completed in 5 minutes. After the formation of the particles was completed, the soluble salts were removed by settling at 35 ° C. Next, the temperature was raised to 40 ° C., and 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and the pH was adjusted to 6.8 with sodium hydroxide. The obtained emulsion had a finished amount of 73.
Monodispersed AgI fine particles having an average diameter of 0.015 μm were obtained at 0 g.

Using the emulsions AF, T and U as described below, comparative photosensitive elements (sample 101) having the constitutions shown in Tables 2 to 5 below were prepared. At the end of the shell chemical sensitization, the sensitizing dye was added at the dye type, dispersion form, addition temperature and amount shown in Table 6 below.

[0161]

[Table 2]

[0162]

[Table 3]

[0163]

[Table 4]

[0164]

[Table 5]

[0165]

[Table 6]

[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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Preparation of a cover sheet A transparent support having a thickness of 75 μm was applied in a layer constitution as shown in Table 7 to prepare a cover sheet.

[0180]

[Table 7]

The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

[0182]

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[0183]

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The formula of the alkali treatment composition is shown below. Silver nitrate 0.10 g Carbon black (manufactured by Dainichi Seika Co., Ltd.) 160 g Additive (22) 8.60 g Carboxymethyl cellulose Na salt 58.0 g Benzyl alcohol 2.50 g Additive (23) 2.10 g Potassium sulfite (anhydrous ) 1.90 g 5-methylbenzotriazole 2.50 g 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 7.00 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10 0.06 g Potassium hydroxide 56.0 g Aluminum nitrate 0.60 g Zinc nitrate 0.60 g Additive (24) 6.60 g Additive (14) 1.80 g 1,2-Benzisothiazolin-3-one 0.003 g

[0185]

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To each of the high-sensitivity blue, green and red light-sensitive layers of the light-sensitive material 101, the compounds and amounts shown in Table 8 were added, and the average particle size of the color mixture preventing layer emulsion was adjusted. Photosensitive materials 101 to 101
112 was produced. As described above, the activity of the color mixing prevention ability changes depending on the particle size of the intermediate layer emulsion. For this reason, 25
The application amount of the hydroquinone derivative was changed so that the maximum concentration at the time of the standard treatment at ° C became equal.

[0187]

[Table 8]

Next, the photosensitive materials 101 to 112 were exposed from the emulsion layer side through a gray continuous wedge, and then superposed on the cover sheet. The alkali treatment composition was pressed between both materials so as to have a thickness of 62 μm. Deployed using rollers. After 2 hours at 25 ° C., the transfer density of the highest density portion of each color of yellow, magenta, and cyan was determined.
The fog of the lowest density portion was measured with a color densitometer. Further, the time until the appearance of the image after processing was measured. In addition, to evaluate the photographic properties change due to storage of the photosensitive material, the photosensitive material should be kept at 35 ° C.
The maximum concentration after storage at 80% for 7 days (7d) was measured. Table 9 summarizes the measurement results.

[0189]

[Table 9]

As can be seen from Table 9, the transfer density of the highest density part at 2 hours after the treatment was sufficient for all samples, but the oxidizing agents of the general formulas (I) to (III) of the present invention were added. However, Comparative Example Samples 102 to 104 in which the particle size of the reducing agent loaded particles in the color mixture prevention layer is 0.2 μm or more.
The image appearance time is long (slow). On the other hand, even if the emulsion particle size is 0.2 μm or less, Comparative Examples 105 and 10 which do not use the compound of the general formula (I), (II) or (III)
In No. 6, the image appearance time is not shortened, and the color density greatly decreases over time. On the other hand, Samples 107 to 112 of the present invention, in which the compounds of the general formulas (I), (II) or (III) were used and the color-mixing preventive particles were also made finer, had a fast image appearance and sufficient It was shown that a photosensitive material having a maximum density, suppressing stain, and having a small change in density during storage was obtained.

Example 2 In the above-mentioned Example 1, 49 μl of the alkali-treated composition was used.
When the same experiment as in Example 1 was performed except that the image was developed so as to obtain m, the image appearance time was short due to the combination of the compound of the present invention and the intermediate layer, and It was found that a light-sensitive material having a small density fluctuation was obtained.

Example 3 A photosensitive element 201 was prepared by coating on a 100 μm transparent polyethylene terephthalate film support in the following manner. Back layer side: (a) A light-shielding layer containing 6.0 g / m 2 of carbon black and 2.0 g / m 2 of gelatin. (B) A protective layer containing 0.5 g / m @ 2 of gelatin. Emulsion layer side: (1) Titanium dioxide 3.7 g / m 2 and gelatin 0.
A layer containing 5 g / m2. (2) The following cyan dye releasing redox compound 0.46
g / m 2, 0.07 g of tricyclohexyl phosphate
/ M 2, a coloring material layer containing the following dispersing aid (A) 0.05 g / m 2, the following dispersing aid (B) 0.06 g / m 2, and gelatin 0.5 g / m 2.

[0193]

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(3) A layer containing 0.5 g / m 2 of gelatin. (4) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 .mu.m, silver amount: 0.11 g / m @ 2), gelatin: 0.3 g / m @ 2, nucleating agent described below: 0.003 g / m @ 2 And a red-sensitive emulsion layer containing 0.02 g / m @ 2 of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

[0195]

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(5) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, 0.23 g / silver amount)
m2), gelatin 0.4 g / m2, 2-sulfo-5-n
Pentadecylhydroquinone sodium salt 0.04
g / m 2, and 0.005 mg of the same nucleating agent as in layer (4)
/ M @ 2 containing a red-sensitive emulsion layer. (6) 2,5-di-t-pentadecylvidroquinone 0.61 g / m 2, the following polymer dispersant 0.33 g /
a color mixing preventing layer containing m2 and gelatin at 0.3 g / m2.

[0197]

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(7) An intermediate layer containing 0.2 g / m 2 of gelatin. (8) The following magenta dye-releasing redox compound is used in 0.1.
46 g / m @ 2, the same dispersing aid (A) as layer (2) 0.04
g / m2, a colorant layer containing 0.07 g / m2 of the dispersing aid (B) and 0.7 g / m2 of gelatin.

[0199]

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(9) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.11 g /
m2), gelatin 0.2 g / m2, the same nucleating agent as in layer (4) 0.005 mg / m2 and 2-sulfo-5-n-pentadasylhydroquinone sodium salt 0.02 g / m2
Green-sensitive emulsion layer containing m2. (10) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.26 g / m 2), gelatin 0.6 g / m 2, nucleating agent same as layer (4) 0 .004
A green-sensitive emulsion layer containing mg / m2 and 0.04 g / m2 of sodium 2-sulfo-5-n-pentadecylhydroquinone salt. (11) 2,5-di-t-pentadecyl hydroquinone 0.91 g / m 2, the following polymer dispersant 0.29 g /
an anti-color mixing layer containing m2 and gelatin at 0.4 g / m2.

[0201]

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(12) The same layer as in (7). (13) Yellow dye releasing redox compound having the following structure: 0.53 g / m 2, tricyclohexyl phosphate 0.16 g / m 2, the same dispersing aid (A) as in layer (2)
A coloring material layer containing 0.05 g / m @ 2, 0.03 g / m @ 2 of dispersing aid (B) and 0.5 g / m @ 2 of gelatin;

[0203]

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(14) Blue-sensitive inner latent type positive-contact silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.15 g /
m2), gelatin 0.2 g / m2, the same nucleating agent as layer (4) 0.006 mg / m2 and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.01 g / m2).
Blue-sensitive emulsion layer containing m2. (15) Blue-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.23 g / m 2), gelatin 0.3 g / m 2, nucleating agent 0 same as layer (4) .005
mg / m @ 2 and 0.01 g / m @ 2 of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. (16) The following UV absorbers (A) and (B)
An ultraviolet absorbing layer containing 2 g / m @ 2 and 0.5 g / m @ 2 gelatin.

[0205]

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(17) Matting agent (PMMA) 0.2 g /
m2, the following hardener (A) 0.11 g / m2, the following hardener (B) 0.03 g / m2 and gelatin 0.4 g / m2
A protective layer containing m2.

[0207]

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Next, an image receiving element (301) was prepared by applying the following layer composition on a 150 μm paper support having 20 μm polyethylene laminated on both sides.

Back layer side: (a) A light-shielding layer containing 2.8 g / m 2 of carbon black and 4.8 g / m 2 of gelatin. (B) 4.1 g / m 2 of titanium dioxide and gelatin 1.
White layer containing 0 g / m2. (C) A protective layer containing 0.5 g / m @ 2 of gelatin. Image receiving layer side: (1) Acrylic acid / butyl acrylate copolymer (molar ratio 8: 2, average molecular weight 50,000) 4.0 g / m 2,
Polyvinyl alcohol (polymerization degree 500, saponification rate 88%)
And a neutralizing layer containing 0.04 g / m 2 of the following compound (F).

[0210]

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(2) Diacetyl cellulose (degree of acetylation: 5
(1.3%) 3.5 g / m @ 2, styrene / maleic anhydride copolymer (molar ratio 1: 1, average molecular weight 10,000)
39 g / m2, the following compound (B) 0.07 g / m2, and Colonnade HL (manufactured by Nippon Polyurethane Co., Ltd.) 0.0
Timing layer containing 98 g / m2.

[0212]

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(3) Polymer latex (styrene / butyl acrylate / N-methylol acrylamide emulsion-polymerized at a weight ratio of 49.7 / 42.3 / 8)
1.32 g / m @ 2 and a polymer latex (emulsion-polymerized methyl methacrylate / acrylic acid / N-methylolacrylamide at a weight ratio of 93/3/4) 1.3
A timing layer containing 2 g / m 2, 0.162 g / m 2 of the following compound (C), and 0.0148 g / m 2 of the following coating aid (D).

[0214]

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(5) The following mordant (E): 3.7 g / m 2,
0.21 g / m 2 of formaldehyde, 0.10 g / m 2 of the hardener (F), 0.01 of the coating aid (D)
mordant layer containing g / m 2 and gelatin 2.8 g / m 2.

[0216]

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(6) Acrylic acid / butyl methacrylate copolymer (molar ratio: 85:15, average molecular weight: 100,00
0) 0.06 g / m 2 and the following compound (H) 0.00
Release layer containing 3 g / m2.

[0218]

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Further, an alkali treatment composition was prepared in which 1 g of a treatment solution having the following composition was filled in an aluminum foil pod laminated with vinyl chloride under a nitrogen atmosphere.

Hydroxyethyl cellulose 42 g Zinc nitrate / 6H2 O 0.9 g 5-Methylbenzotriazole 5.4 g Benzyl alcohol 3.4 cc Titanium dioxide 1.2 g Aluminum nitrate / 9H2 O 15 g Potassium sulfite 1.0 g 1-phenyl-4-hydroxy -4-Hydroxymethyl-3-pyrazolidone 13.0 g Potassium hydroxide 63 g Water 854 cc

Next, after the image-wise exposure was given to the photosensitive element (301), the image-receiving element (301) was overlaid, and an alkali treatment composition was developed between the two elements so as to have a thickness of 60 μm. The processing was performed at 25 ° C., and the photosensitive element and the image receiving element were separated 90 seconds after the processing.

In the above light-sensitive element, the red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer are represented by the general formula (I) relating to the present invention.
When the compound of formula (III) to (III) was added and the above-described layer of the color mixture preventing agent dispersed in the form of fine particles was used, a sufficient maximum density was obtained as in Example 1, and the density fluctuation during storage was small. It turned out that the material was obtained.

[0223]

According to the present invention, a color diffusion transfer photosensitive material in which the image appearance time is short, a sufficient maximum density is obtained, and the density fluctuation during storage is small, and a color diffusion transfer material incorporating the same. A film unit is obtained.

Claims (3)

[Claims] 1. A non-diffusible dye image-forming compound which forms or releases a diffusible dye or its precursor in association with silver development on a support or a dye image forming compound which changes its diffusivity itself. In a color diffusion transfer photosensitive material having at least two photosensitive silver halide emulsion layers combined with a compound, a hydrazine-based nucleating agent is added to the photosensitive silver halide emulsion layer or at least one other hydrophilic colloid layer. The following general formula (I) capable of oxidizing the nucleating agent:
A dispersion of a non-diffusible reducing agent containing at least one of the compounds represented by formulas (III) to (III) and having an average grain size of 0.2 μm or less between at least two photosensitive silver halide emulsion layers. A color diffusion transfer photosensitive material comprising a color mixture prevention layer formed by applying a color mixture. Embedded image In the formula (I), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. Represents a substituted alkoxy group, a substituted or unsubstituted alkylthio group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a halogen atom or a cyano group. R ¹¹ and R ¹² or R ¹³ and R ¹⁴
May be connected to each other to form a ring. Embedded image In the formula (II), D ¹ and D ² may be the same or different from each other and represent an atomic group necessary for forming a benzene ring or a naphthalene ring. G ¹ and G ² may be the same or different and each represents a hydrogen atom or any substituent that does not adversely affect the photograph. A ¹ , A ² and A ³ may be the same or different and each represents a hydrogen atom or any substituent which does not adversely affect the photograph. B ¹ , B ² and B ³ may be the same or different and each represents a hydrogen atom or any substituent that does not adversely affect the photograph. L ¹ and L ² may be the same or different and represent a linking group, and m and n each represent 1 or 0. M ¹ and M ² may be the same or different from each other, and as a result of development, (I)
A component having a function of releasing an azo compound from the compound of I) or a hydrogen atom. Embedded image In the formula (III), EAG represents an electron-accepting group. N and O represent a nitrogen atom and an oxygen atom, respectively. The nitrogen-oxygen atom is cleaved by the EAG receiving an electron from the reducing agent. R ³¹ and R ³² each represent a substituent other than a hydrogen atom that does not adversely affect the photograph. R ³¹ and R ³² , R
³¹ and EAG, R ³² and EAG may be bonded to each other to form a ring. 2. A transparent support comprising an image receiving layer, a white reflective layer, a light-shielding layer, and a photosensitive silver halide emulsion layer combined with the dye image forming compound, wherein the emulsion layer or at least one other hydrophilic layer is provided. Formula (I), (II) or
A photosensitive sheet (A) containing the compound represented by (III),
A transparent cover sheet (B) having at least a neutralization layer and a neutralization timing layer on a transparent support, and arranged so as to be developed between the photosensitive sheet (A) and the transparent cover sheet (B). The color diffusion transfer photosensitive material according to claim 1, which is a color diffusion film unit comprising a light-shielding alkali treatment composition (C). 3. An image receiving sheet (A) comprising at least a neutralizing layer, a neutralizing timing layer, an image receiving layer and a release layer on a support, and a dye-image forming compound on a support provided with a light-shielding property. (B) a light-sensitive sheet containing the compound described above or between the light-sensitive silver halide emulsion layers or at least one other of the light-sensitive silver halide emulsion layers, and the image-receiving sheet (A) and the light-sensitive sheet ( The color diffusion transfer photosensitive material according to claim 1, which is a color diffusion transfer film unit comprising an alkali treatment composition (C) arranged so as to be developed during B).