JP2005300763A - Diffusion transfer film unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color diffusion transfer film unit which ensures high maximum density, low fog and rapid diffusion transfer. <P>SOLUTION: The diffusion transfer film unit is obtained by disposing a photosensitive sheet having on a transparent support an image receiving layer, a white reflective layer, a light shielding layer and a silver halide emulsion layer combined with a dye image forming material, a transparent cover sheet having on a support a neutralization layer and a neutralization timing layer, and a carbon-black-containing alkali processing composition spread between the photosensitive sheet and the transparent cover sheet so that exposure is performed through the transparent cover sheet, wherein at least one compound selected from the compounds represented by formula (I) and at least one compound selected from the compound group represented by formulae (II-1)-(II-4) are contained in the alkali processing composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a diffusion transfer film unit. More specifically, the present invention relates to an integrated color diffusion transfer film unit. The present invention also relates to a color diffusion transfer film unit having a high maximum density, low fog, and fast diffusion transfer.

  The color diffusion transfer film unit includes an integral type and a divided type. One typical example of the split type is a so-called peel-apart type, in which the photosensitive element and the dye-receiving element are coated on different supports, and after image exposure, the photosensitive element and the dye-receiving element are separated. The dye image transferred to the dye image-receiving layer is obtained by superimposing and developing the treatment composition between them, and then peeling off the dye image-receiving element. The feature of this embodiment is that the dye image can be directly observed instead of observing the image through the support as in the case of the integrated type described later, and shows excellent color reproducibility without deterioration in image quality. However, in this embodiment, there is an inconvenience in operation in which the photosensitive element and the image receiving element are superposed in the camera, and an inconvenience in handling the processed film in which the alkaline processing liquid is sticky and easily adheres to the periphery after peeling. is there.

  In this operation, the one that improves inconvenience in handling is an integrated form. An integral diffusion transfer film unit is disclosed in Research Disclosure, 1976, Vol. 15162, Photographic Science and Engineering, July 18, 1976, Vol. 20, No. 4, etc. are well known. In the integrated type, a dye image-receiving element, a photosensitive element, and a neutralization timing element are coated between a transparent support and the other support, and the photosensitive element is coated on the same transparent support as the image-receiving element. And a form coated on another support (hereinafter referred to as the latter).

  In the former case, a white reflective layer is coated between the image-receiving element and the photosensitive element, and in the latter case, the image-receiving layer is formed by adding a white pigment to the processing composition developed between the image-receiving element and the photosensitive element. The dye image transferred to can be observed with reflected light. The present invention relates to the former form, a photosensitive sheet having at least one silver halide emulsion layer combined with at least one dye image forming material on a transparent support, an image receiving layer, a white reflective layer, a light shielding layer, and a transparent support. Color diffusion transfer comprising a transparent cover sheet having at least a neutralization layer and a neutralization timing layer on the body, and a light-shielding alkaline treatment composition developed between the photosensitive sheet and the transparent cover sheet The film unit.

  The integrated diffusion transfer film unit is widely used not only by professionals but also by general amateur users. These users have a strong desire to see images taken or printed out quickly, and it is important to increase the diffusion transfer speed of the color diffusion transfer film unit in order to realize this demand. In order to increase the diffusion transfer speed of the color diffusion transfer film unit, it is effective to increase the silver developing activity, but at the same time there is a problem that the fog increases.

  In order to solve this problem, a method of incorporating a development inhibitor into an alkali processing composition is conventionally known. Conventional development inhibitors include (a) compounds disclosed in JP-A Nos. 5-127332 and 2000-347373, and (b) mercapto groups disclosed in JP-A 2000-305233. And the like.

  However, the compound (a) has to be added in a large amount in order to sufficiently reduce the fog, and has the disadvantage that the maximum concentration is lowered and the diffusion transfer is delayed due to the addition of a large amount. Concerning b), when added to an alkali treatment composition containing carbon black, the fog rises conversely, so it has been considered that it cannot be added to an alkali treatment composition containing carbon black until now. A solution was sought. In particular, color diffusion transfer film units composed of negative silver halides with high silver development activity and fast diffusion transfer speed tend to have higher fog than positive types, and there is a strong demand for solutions to these problems. It was.

Research Disclosure, 1976, Volume 151 No. 15162 Photographic Science and Engineering, July 18, 1976, Volume 20, Issue 4 Japanese Patent Laid-Open No. 5-127332 JP 2000-347373 A JP 2000-305233 A

  Accordingly, an object of the present invention is to provide a color diffusion transfer diffusion film unit having a high maximum density, low fog, and quick diffusion transfer.

（式中、Ｑは炭素原子、窒素原子、酸素原子および硫黄原子からなる群より選ばれる少なくとも１種の原子を構成要素とする５員または６員の複素環を形成するために必要な原子群を表し、該含窒素複素環は置換基を有していてもよいが、置換基としてメルカプト基を有することはない。Ｍは水素原子、アルカリ金属原子、四級アンモニウム基、またはアルカリ条件下で水素原子もしくはアルカリ金属原子となりうる基を表し、ｎは０又は１を表す。）

（式中、Ｑ1、Ｑ2、Ｑ3、Ｑ4またはＱ5は、置換基を有してもよい５員もしくは６員の複素環を形成するために必要な原子群、または置換基を有してもよいベンゼン環と縮合した５員もしくは６員の複素環を形成するために必要な原子群を表す。Ｒ1は置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、および置換もしくは無置換のアラルキル基からなる群より選ばれる基を表す。Lは水素原子またはアルカリ金属原子を表す。）
（２）（１）に記載の拡散転写フイルムユニットにおいて、一般式（II−1）〜（II−4）で表される化合物群より選ばれる少なくとも1種の化合物が、一般式（II−1）で表される化合物であることを特徴とする拡散転写フイルムユニット、
（３）（１）または（２）に記載の拡散転写フイルムユニットにおいて、該拡散転写フイルムユニット感光シート中のハロゲン化銀乳剤が、ネガ型ハロゲン化銀乳剤であることを特徴とする拡散転写フイルムユニット、
（４）（１）または（２）に記載の拡散転写フイルムユニットにおいて、 該拡散転写フイルムユニット感光シート中のハロゲン化銀乳剤が、内部潜像型直接ポジハロゲン化銀乳剤であることを特徴とする拡散転写フイルムユニット、
（５）（１）〜（４）のいずれかに記載の拡散転写フイルムユニットにおいて、複数個の特定波長域で発光する異なる光源を有する露光ヘッドを用いて露光されることを特徴とする拡散転写フイルムユニット、
により達成された。 The above issues
(1) An image-receiving layer, a white reflective layer, a light-shielding layer, a photosensitive sheet having a silver halide emulsion layer combined with a dye image-forming substance on a transparent support, and a neutralization layer and a neutralization timing layer on the support A transparent cover sheet, and a carbon black-containing alkali treatment composition developed between the photosensitive sheet and the transparent cover sheet, in a diffusion transfer film unit arranged so that these are exposed through the transparent cover sheet, the following general formula Both at least one compound selected from the compounds represented by (I) and at least one compound selected from the compound groups represented by the following general formulas (II-1) to (II-4): A diffusion transfer film unit comprising the alkali treatment composition;

(In the formula, Q is an atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring having at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a constituent element) The nitrogen-containing heterocycle may have a substituent, but does not have a mercapto group as a substituent, and M is a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or an alkaline condition. A hydrogen atom or a group which can be an alkali metal atom, and n represents 0 or 1)

(In the formula, Q1, Q2, Q3, Q4 or Q5 may have a group of atoms or a substituent necessary for forming a 5-membered or 6-membered heterocyclic ring which may have a substituent. A group of atoms necessary for forming a 5- or 6-membered heterocyclic ring condensed with a benzene ring, wherein R1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl. Represents a group selected from the group consisting of groups, L represents a hydrogen atom or an alkali metal atom.)
(2) In the diffusion transfer film unit according to (1), at least one compound selected from the group of compounds represented by the general formulas (II-1) to (II-4) is represented by the general formula (II-1): A diffusion transfer film unit characterized by being a compound represented by
(3) The diffusion transfer film unit according to (1) or (2), wherein the silver halide emulsion in the diffusion transfer film unit photosensitive sheet is a negative silver halide emulsion. unit,
(4) The diffusion transfer film unit according to (1) or (2), wherein the silver halide emulsion in the photosensitive sheet of the diffusion transfer film unit is an internal latent image type direct positive silver halide emulsion. Diffusion transfer film unit,
(5) The diffusion transfer film unit according to any one of (1) to (4), wherein the exposure is performed using an exposure head having different light sources that emit light in a plurality of specific wavelength regions. Film unit,
Achieved by.

  According to the present invention, a diffusion transfer film unit having a high maximum density, low fog, and quick diffusion transfer can be provided.

  The compounds represented by the general formulas (II-1) to (II-4) are disclosed in JP-A-2000-305233, JP-T-11-509649, etc. Only the composition is described. There is no description about the alkali treatment composition containing carbon black as a light-shielding agent. If the above compound is added alone in an alkali treatment composition containing carbon black as a light-shielding agent, the fog rises. The inventors of the present invention can reduce fog without lowering the maximum density or delaying diffusion transfer by using the above compound together with the compound of the general formula (I) in an alkali treatment composition containing carbon black as a light-shielding agent. I found out that I can. When the compound of the above general formulas (II-1) to (II-4), which increases the fog when added, together with the compound of the general formula (I), the fog of the diffusion transfer film unit is reduced. It is surprising and unexpected from conventional knowledge.

  The compound represented by the general formula (I) described in claim 1 will be described in detail below.

  In the formula, Q represents an atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring composed of at least one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. The nitrogen-containing heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. Further, the nitrogen-containing heterocycle may have a substituent, but does not have a mercapto group as a substituent.

  Specific examples of the heterocyclic ring formed by Q include indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzthiazole ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, tetrazole ring, azaindene ring, Examples include pyrazole ring, indole ring, triazine ring, pyrimidine ring, pyridine ring, quinoline ring and the like.

  These heterocyclic rings are a nitro group, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, and a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a t-butyl group, a cyanoethyl group, Methoxyethyl group, methylthioethyl group etc.), aryl group (eg phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group etc.), alkenyl group (eg allyl group etc.) ), Aralkyl groups (eg benzyl group, 4-methylbenzyl group, phenethyl group etc.), alkoxy groups (eg methoxy group, ethoxy group etc.), aryloxy groups (eg phenoxy group, 4-methoxyphenoxy group etc.), alkylthio groups (Eg, methylthio group, ethylthio group, methoxyethylthio group, etc.), aryl Thio group (for example, phenylthio group), sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (For example, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (for example, acetamido group, benzamide group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, p -Toluenesulfonamide group)

Acyloxy groups (eg acetyloxy group, benzoyloxy group etc.), sulfonyloxy groups (eg methanesulfonyloxy group etc.), ureido groups (eg unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group etc.), Thioureido groups (for example, unsubstituted thioureido groups, methylthioureido groups, etc.), acyl groups (for example, acetyl groups, benzoyl groups, etc.), heterocyclic groups (for example, 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4- Pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group, etc.), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group etc.), oxycarbonylamino group ( For example, a methoxycarbonylamino group, Enoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), amino group (for example, unsubstituted amino group, dimethylamino group, methoxyethylamino group, anilino group), carboxylic acid or salt thereof, sulfonic acid or its It may be substituted with a salt, a hydroxy group or the like.

M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), a quaternary ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, tetrabutylammonium group, tetramethylammonium group, etc.), and alkaline conditions. A group (for example, acetyl group, cyanoethyl group, methanesulfonyl group) in which M can be a hydrogen atom or an alkali metal atom by a substitution reaction with the alkali compound or hydrolysis.
Examples of the compound that gives an alkaline condition include a hydroxide of an alkali metal element or a hydroxide of an alkaline earth metal element, preferably a hydroxide of an alkali metal element, more preferably potassium hydroxide. .
Preferred M is a hydrogen atom, an alkali metal atom or a quaternary ammonium group, more preferably a hydrogen atom or an alkali metal atom, and particularly preferably a hydrogen atom.
n represents 0 or 1.

  Of the heterocyclic rings represented by the general formula (I), preferred are benzotriazoles, indazoles and benzimidazoles, and benzotriazoles are particularly preferred.

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

  The compound (I) used in the present invention is Berichte der DeutschenChemischen Gesellschaft 22, 77 (1895), JP 50-37436, 51-3231, US Pat. 295,976, 3,376,310, Berichte der DeutschenChemischen Gesellschaft 22, 568 (1889), 29, 2483 (1896), Journal of Chemical Society (J. Chem. Soc.) 32, 1806, Journal of the American Chemical Society (J. Am. Chem. Soc.) 71, 4000 (1949),

  U.S. Pat. Nos. 2,585,388, 2,541,924, Advisory in Heterocyclic Chemistry 9, 165 (1968), Organic Synthesis IV, 569 (1963), Journal of the American Chemical Society (J. Am. Chem. Soc.) 45, 2390 (1923), Hemische Brichte 9, 465 (1876), Japanese Patent Publication No. 40-28496, Special Kaisho 50-89034, U.S. Pat. Nos. 3,106,467, 3,420,760, 2,271,229, 3,137,578, 3,148,066, 3 511,663, 3,060,028, 3,271,154, 3,251,691, 3,598,599 No. 3,148,066, Japanese Patent Publication No. 43-4135, U.S. Pat. Nos. 3,615,616, 3,420,664, 3,071,465, 2,444,605, 2,444,606, 2,444,607, 2,935,404, JP-A-57-202,531, 57-167,023, 57-164,735, 60-80839, 58-152,235, 57-14836, 59-162,546, 60-130,731, 60-138,548, 58-83852, 58-159,529, 59-159,162, 60-217,358, 61-80238, JP-B 60-29390, 60-29391, 60-133,061, 60-143 It can be synthesized by the method described in issue like.

The addition amount of the processing solution of the compound represented by the general formula (I) used in the present invention is preferably 0.01mmol / m ² ~10.0mmol / m ² The coating amount at the time of deployment, particularly 0.1mmol / M ^{2 to} 5.0 mmol / m ² is preferable. The compound represented by the general formula (I) used in the present invention may be added to the processing solution only one kind, but two or more kinds may be added, or other conventionally known development inhibitors. Can also be used together.

  Next, the compounds represented by formulas (II-1) to (II-4) used in the present invention will be described in detail.

  In the formula, Q1 to Q5 may be the same as or different from each other, and may have a substituent. Represents a group of atoms necessary to form a heterocyclic ring. Examples of the heterocyclic ring include pyrrole ring, pyrazole ring, imidazole ring, imidazoline ring, benzimidazole ring, benzimidazoline ring, triazole ring, tetrazole ring, thiazole ring, thiazoline ring, benzothiazole ring, naphthothiazole ring, benzothiazoline ring, Examples include an oxazole ring, an oxazoline ring, a benzoxazole ring, a benzoxazoline ring, a pyridine ring, a pyrimidine ring, a triazine ring, a pyrazine ring, a thiazine ring, an oxazine ring, a thiadiazole ring, an oxadiazole ring, and a tetraazaindene ring. Examples of the substituent of the heterocyclic ring include substituted or unsubstituted alkyl groups (for example, methyl group, ethyl group, octyl group, hydroxyethyl group, methoxyethyl group, dimethylaminoethyl group, ethoxycarbonylethyl group, acyloxyethyl group, methylthio group). Ethyl group, morpholinomethyl group, etc.), allyl group, substituted or unsubstituted aryl group (for example, phenyl group, naphthyl group, caproamidophenyl group, nitrophenyl group, chlorophenyl group, methylphenyl group, ethoxyphenyl group, methane) Sulfonylphenyl group, carboxyphenyl group, sulfoxyphenyl group, carbamoylphenyl group, dimethylaminophenyl group, etc.), substituted or unsubstituted aralkyl groups (eg benzyl group, chlorobenzyl group, methoxybenzyl group etc.), halogen atoms (eg Black Bromo, iodo, etc.), nitro group, substituted or unsubstituted alkoxy group (eg methoxy group, ethoxy group, methoxyethoxy group etc.), substituted or unsubstituted aryloxy group (eg phenoxy group, methylphenoxy group, chlorophenoxy) Group), substituted or unsubstituted alkylthio group (for example, methylthio group, methoxyethylthio group, hydroxyethylthio group, etc.), substituted or unsubstituted arylthio group (for example, phenylthio group, carboxyphenylthio group, naphthylthio group, etc.),

_{-COOM 11, -COOR 11, -SO 3} M 11, -SO 3 R 11, -SO-R 11, -SO 2 R 11, -NH 2, -NHR 11, -N (R 11) (R 12) _{, -NHCOR 11, -NH · CO ·} NH · R 11, -NHCO 2 R 11, -CONH-R 11, -CONH 2, -SO 2 NH 2, -SO 2 NHR 11, {M 11 represents a hydrogen atom, NH ₄ or an alkali metal atom such as sodium atom or potassium atom, R ₁₁ and R ₁₂ are substituted or unsubstituted alkyl group, aryl group, aralkyl group, heterocyclic group (for example, pyridine ring, thiadiazole ring, imidazole ring, etc.) ). } Etc. can be mentioned. These substituents preferably have 8 or less carbon atoms.

  R1 represents a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, octyl group, hydroxyethyl group, methoxyethyl group, dimethylaminoethyl group, ethoxycarbonylethyl group, acyloxyethyl group, methylthioethyl group, morpholinomethyl group, etc.) , Preferably 7 or less in total carbon number), substituted or unsubstituted aryl group (for example, phenyl group, naphthyl group, caproamidophenyl group, nitrophenyl group, aminophenyl group, chlorophenyl group, methylphenyl group, ethoxyphenyl group) , Methanesulfonylphenyl group, carboxyphenyl group, sulfoxyphenyl group, carbamoylphenyl group, dimethylaminophenyl group, etc., preferably 10 or less in total carbon number) or substituted or unsubstituted aralkyl group (for example, benzyl group, chlorobenzyl group, Meto A xylbenzyl group and the like, preferably a total number of carbon atoms of 10 or less). L represents a hydrogen atom or an alkali metal atom (sodium atom, potassium atom, etc.).

  Specific examples of the compounds represented by formulas (II-1) to (II-4) used in the present invention are shown below, but the present invention is not limited thereto.

  Among the compounds represented by the general formulas (II-1) to (II-4) used in the present invention, preferred are compounds represented by the general formula (II-1), and particularly preferred Are A-28 to A-33 in the above specific examples.

The addition amount of the compounds represented by the general formulas (II-1) to (II-4) used in the present invention to the treatment liquid is from 0.0001 mmol / m ^{2 to} 10.0 mmol / m as a coating amount at the time of development. ² is preferable, and 0.001 mmol / m ^{2 to} 1.0 mmol / m ² is particularly preferable. Only one type of the compounds represented by the general formulas (II-1) to (II-4) used in the present invention may be added to the treatment liquid, but two or more types may be added. It can also be used in combination with other development inhibitors.

  Examples of each component that can be used in the diffusion transfer film unit of the present invention will be described below.

I. Photosensitive sheet A) Support The support of the photosensitive sheet used in the present invention is any smooth transparent support that is usually used in photographic photosensitive materials, and cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, and the like are used. An undercoat layer (undercoat layer) is preferably provided. In general, the support preferably contains a trace amount of a dye or a pigment such as titanium oxide in order to prevent light piping. The thickness of the support of the photosensitive sheet is 25 to 350 μm, preferably 50 to 210 μm, more preferably 70 to 150 μm. If necessary, a layer for curling balance or an oxygen barrier layer described in JP-A-56-78833 can be provided on the back side of the support.

B) Image receiving layer The image receiving layer (dye image receiving layer) of the photosensitive sheet used in the present invention includes a mordant contained 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. These are described in JP-A-61-252551. As the mordant, a polymer mordant is preferable.
The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation, etc., having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Is. The coating amount of the mordant is generally 0.5 to 10 g / m ^2, preferably 1.0 to 5.0 g / m ^2, particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used for the image receiving layer of the photosensitive sheet, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred.
In the image receiving layer, anti-fading agents described in JP-A Nos. 62-30620, 62-30621, and 62-215272 can be incorporated.
The thickness of the image receiving layer used in the present invention is not particularly limited.

C) White reflective layer The white reflective layer of the photosensitive sheet used in the present invention may form a white background of a color image, but usually contains a white pigment and a hydrophilic binder.
As the white pigment for the white reflective layer, barium sulfate, zinc oxide, barium stearate, silver flakes, silicates, alumina, zirconium oxide, zirconium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Furthermore, non-film-forming polymer particles made of styrene or the like are also used. Moreover, these may be used independently and can also be mixed and used in the range in which the preferable reflectance is obtained.
The white pigment is preferably titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, but the light reflectance is preferably 70% or more.
When using titanium dioxide as a white pigment, titanium dioxide 5 to 40 g / m ^2, preferably 10 to 25 g / m ² was applied, white reflection light reflectance has a 78 to 85% with light having a wavelength of 540nm A layer is preferred. Titanium dioxide can be selected from various commercially available brands.
Of these, rutile type titanium dioxide is particularly preferred. Most of the commercially available products are surface-treated with alumina, silica, zinc oxide or the like, and in order to obtain a high reflectance, a surface treatment amount of 5% or more is preferable. Examples of commercially available titanium dioxide include those described in Research Disclosure Magazine No. 15162 in addition to Ti-pure R931 (trade name) manufactured by DuPont.

As the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, hydroxyethyl cellulose, and cellulose derivatives such as carboxymethyl cellulose can be used. When gelatin is used as the binder, the mass ratio of the white pigment to gelatin is 1/1 to 20/1, preferably 5/1 to 10/1.
It is preferable to incorporate an anti-fading agent such as Japanese Patent Publication Nos. 62-30620 and 62-30621 in the white reflective layer.

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 following photosensitive layer. As the light shielding agent, any material having a light shielding function is used, but carbon black is preferably used. Further, degradable dyes described in US Pat. No. 4,615,966 may be used. The binder for coating the light-shielding agent may be any one that can disperse carbon black, and is preferably gelatin. As the carbon black raw material, any method such as a channel method, a thermal method and a furnace method as described in Donnel Voet “Carbon Black” Marcel Dekker, Inc. (1976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1800 mm. The addition amount of the black pigment as the 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 terms of optical density.
The thickness of the light shielding layer used in the present invention is not particularly limited.

E) Photosensitive layer In the present invention, a photosensitive layer comprising at least one silver halide emulsion layer combined with a dye image forming substance (dye image forming compound) is provided adjacent to 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, 4,139 No. 4,383, No. 4,195,992, No. 4,148,641, No. 4,148,643, No. 4,336,322, JP-A No. 51-114930, No. 56-71072, Research Disclosure 17630 (1978), and 16475 (1977).

Examples of magenta dyes:
U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, 3,954 No. 4,476, No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4,207,104, 4,287,292, JP-A-52-106727, 53-23628, 55-36804, 56-73057, 56-71060, 55-134 , JP-A-7-120901, 8-286343, 8-286344, and 8-292537.

Examples of cyan dyes:
U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220, 4,242 , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138 Japanese Patent Laid-Open Nos. 54-99431, 52-8827, 53-47823, 53-143323, 54-99431, 56-71061; European Patent (EP) 53,037, 53,040; Research Disclosure 17,630 (1978) and 16,475 (1977).

A dye image forming compound that forms a dye by coupling can also be used. For example, they are described in JP-A-8-286340, JP-A-9-152705, JP-A-8-357190, JP-A-8-357191, JP-A-9-117529, and the like.
A positive type dye image forming compound can also be used. In this case, a negative silver halide emulsion may be used as the silver halide emulsion. Examples thereof include JP-A-4-156542, JP-A-4-155332, JP-A-4-172344, JP-A-4-172450, JP-A-4-318844, JP-A-356046, and JP-A-5-45824. Gazette, 5-45825 gazette, 5-53279 gazette, 5-107710 gazette, 5-241302 gazette, 5-107708 gazette, 5-232659 gazette, and U.S. Pat. No. 192,649.

  These compounds can be dispersed by the method described in JP-A-62-215272, pages 144-146. These dispersions may contain the compounds described in JP-A-62-215272, pages 137 to 144. Specific examples of these dye image forming compounds include the following compounds. Dye in the following compounds represents a dye group, a dye group temporarily shortened in wavelength, or a dye precursor group.

(2) Silver halide emulsion The silver halide emulsion used in the present invention may be, for example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide or silver chloroiodobromide. In particular, a negative type silver halide emulsion that forms a latent image on the surface of silver halide grains, or an internal latent image type direct positive emulsion that forms a latent image inside silver halide grains is preferred.

  The negative type emulsion that forms a latent image on the surface of the silver halide grain may be a so-called core-shell emulsion having a phase different from that of the inside of the grain and the surface of the grain, and silver halides having different compositions are joined by epitaxial joining. May be. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167743 and 4-223463 is also used.

  The crystal habit of silver halide grains has regular crystals such as cubes, octahedrons, tetradecahedrons, spherical crystals, irregular crystal systems such as high aspect ratio flat plates, twins Any of those having a crystal defect such as a plane, a composite system thereof, or the like may be used.

  Specifically, US Pat. No. 4,500,626, column 50, 4,628,021, Research Disclosure Journal (hereinafter abbreviated as RD) No. 17, 029 (1978), ibid. 17, 643 (December 1978) 22-23, the same No. 18, 716 (November 1979) 648, ibid. 307, 105 (November 1989) 863-865, JP-A-62-253159, JP-A-64-13546, JP-A-2-236546, JP-A-3-110555, and Grafkide, "Photograph Physics and Chemistry". Published by Paul Monte (P. Glafkides, Chemie et Pisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), Halogens prepared using the method described in “Production and coating of photographic emulsions” by Zerikman et al., Published by Focal Press (V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964), etc. Any silver halide emulsion can be used.

  In the process of preparing a photosensitive silver halide emulsion, it is preferable to perform so-called desalting to remove excess salt. As a means for this, a Nudell water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid) Sodium), or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. A sedimentation method is preferably used.

  The photosensitive silver halide emulsion used in the present invention may contain, for example, heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount added depends on the purpose of use, but is generally about 10-9 to 10-3 mole per mole of silver halide. Moreover, when making it contain, you may put in a particle | grain uniformly and you may make it local in the inside and surface of particle | grains. Specifically, emulsions described in JP-A-2-236542, 1-116637, and 5-181246 are preferably used.

  In the grain formation stage of a light-sensitive silver halide emulsion, rhodan salts, ammonia, tetrasubstituted thioether compounds, organic thioether derivatives described in JP-B-47-11386 or JP-A-53-144319 are described as silver halide solvents. Sulfur-containing compounds can be used.

  As for other conditions, the above-mentioned “Photo Physics and Chemistry” by Grafkide published by Paul Monte (P. Glafkides, Chemie et Pisique Photographique, Paul Montel, 1967), Duffin “Photo Emulsion Chemistry”, published by Focal Press ( GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), “Manufacture and coating of photographic emulsions” by Zerikman et al., Published by Focal Press (V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press , 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used as a form for reacting a soluble silver salt and a soluble halogen salt. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A backmixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is generated is kept constant can be used.

  In order to accelerate grain growth, the addition concentration, addition amount, and addition rate of silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open Nos. 55-142329, 55-158124, US Pat. No. 3,650,757). etc). Furthermore, the stirring method of the reaction solution may be any conventional stirring method. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner according to the purpose. The preferred pH range is 2.3 to 8.5, more preferably 2.5 to 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion.
For chemical sensitization of light-sensitive silver halide emulsions, known emulsions for light-sensitive materials include known sulfur sensitizing methods, selenium sensitizing methods, chalcogen sensitizing methods such as tellurium sensitizing methods, gold, platinum, palladium, etc. The noble metal sensitizing method and the reduction sensitizing method to be used can be used alone or in combination (for example, JP-A-3-110555, JP-A-5-241267, etc.). Such chemical sensitization can also be performed in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253159). An antifoggant can be added after the chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-240446 can be used. The antifoggant represented by formula (A) used in the present invention is preferably added at the end of chemical sensitization.

The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9 .0. The coating amount of the photosensitive silver halide used in the present invention is in the range of terms of silver 1 mg to 10 g / m ^2, preferably a 10mg~10g / m ^2.

  In order to give the photosensitive silver halide used in the present invention green sensitivity, red sensitivity, and blue sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. Moreover, you may give infrared-sensitive spectral sensitization as needed.

  The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180,550, JP-A-64-13546, JP-A-5-45828, and JP-A-5-45834. Is mentioned. These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization.

In addition to the sensitizing dye, a dye that does not itself have spectral sensitizing action or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion before or after chemical ripening, or before or after nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. Good. These sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant solution. The amount added is generally about 10 ⁻⁸ to 10 ⁻² mole per mole of silver halide.

  Internal latent image type direct positive emulsions include, for example, so-called “conversion type” emulsions made by utilizing the difference in solubility of silver halide, metal ions doped, chemically sensitized, or both. There is a “core / shell type” emulsion in which at least the photosensitive sites of the inner core (core) grains of the silver halide applied are coated with an outer shell (shell) of silver halide. 592,250, 3,206,313, British Patent 1,027,146, US Patents 3,761,276, 3,935,014, 3,447,927, 2, 297,875, 2,563,785, 3,551,662, 4,395,478, West German Patent 2,728,108, US Pat. No. 4,431,730, etc. ing

  When an internal latent image type direct positive emulsion is used, it is necessary to give surface fog nuclei using light or a nucleating agent after image exposure. As the nucleating agent therefor, hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982, hydrazines and hydrazones described in US Pat. No. 3,227,552, UK Patent 1,283,835, JP-A-52-69613, US Patent 3,615,615, 3,719,494, 3,734,738, 4,094,683, Heterocyclic quaternary salt compounds described in U.S. Pat. No. 4,115,122, and sensitizing dyes having a nucleating substituent described in U.S. Pat. No. 3,718,470 in dye molecules, U.S. Pat. , 030,925, 4,031,127, 4,245,037, 4,255,511, 4,266,013, 4,276,364, British Patent 2, 012,443 etc. Thiourea-linked acylhydrazine compounds and heterocyclic groups such as thioamide rings, triazoles, and tetrazoles described in US Pat. Nos. 4,080,270, 4,278,748, British Patent 2,011,391B, etc. An acyl hydrazine-based compound in which is bonded as an adsorbing group is used.

  In the present invention, a spectral sensitizing dye can be used in combination with these negative emulsion and internal latent image type direct positive emulsion. Specific examples thereof include JP-A-59-180550, JP-A-60-140335, Research Disclosure (RD) 17029, U.S. Pat. No. 1,846,300, JP-A-2,078,233, JP-A-2,089, No. 129, No. 2,165,338, No. 2,231,658, No. 2,917,516, No. 3,352,857, No. 3,411,916, No. 2,295,276 2,481,698, 2,688,545, 2,921,067, 3,282,933, 3,397,060, 3,660,103, 3,335,010, 3,352,680, 3,384,486, 3,623,881, 3,718,470, 4,025,349, etc. ing.

(3) Structure of photosensitive layer The above-described dye image-forming compound which provides a dye having a selective spectral absorption in the same wavelength range as that of the emulsion spectrally sensitized by the spectral sensitizing dye for reproducing a natural color by the subtractive color method And a photosensitive layer comprising at least two of the combinations.
The emulsion and the dye image-forming compound may be applied as separate layers, or may be mixed and applied as a single layer. When the dye image-forming compound 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 formed. The sensitivity of the provided photosensitive element can also be increased.

Such a reflective 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 ^{0.1g / m 2 ~8g / m 2} , and preferably from ^{0.2g / m 2 ~4g / m 2} . An example of the reflective layer is described in JP-A-60-91354.

In the multilayer structure of the photosensitive layer in the present invention, it is preferable that the combination unit of the blue-sensitive emulsion, the combination unit of the green-sensitive emulsion, and the combination unit of the red-sensitive emulsion are sequentially arranged from the exposure side. Arbitrary layers can be provided between the respective emulsion layer units as required. In particular, it is preferable to provide an intermediate layer in order to prevent the undesired influence of the development effect of a certain 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 coated as necessary.
The thickness of the photosensitive layer in the present invention is not particularly limited.

II. Transparent cover sheet In the color diffusion transfer film unit of the present invention, it is preferable to have a neutralizing function on the transparent cover sheet.
F) Support The support of the cover sheet used in the present invention may be any smooth transparent support that is usually used for photographic materials, and cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, etc. are used, and an undercoat is used. It is preferred to provide a layer. The support preferably contains a trace amount of dye to prevent light piping.

G) Layer having a neutralization function The layer having a neutralization function (neutralization layer) used in the present invention contains an acidic substance in an amount sufficient to neutralize the alkali introduced from the alkali treatment composition described later. It may be a layer having a multilayer structure composed of layers such as a neutralization rate adjusting layer (neutralization timing layer) and an adhesion reinforcing layer, if necessary.
A preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis), more preferably olein described in US Pat. No. 2,983,606. Higher fatty acids such as acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. No. 3,362,819; French Patent 2,290 Copolymer of acrylic acid and acrylate ester as disclosed in US Pat. No. 4,699; Research Disclosure No. 4,139,383 and Research Disclosure No. Mention may be made of latex-type acidic polymers as disclosed in US Pat. No. 16102 (1977). In addition, U.S. Pat. No. 4,088,493, JP-A-52-153739, 53-1023, 53-4540, 53-4541, 53-4542, etc. Mention may also be made of the disclosed acidic substances.

  Specific examples of the acidic polymer (polymer acid) as the acidic substance include a copolymer of vinyl monomer such as ethylene, vinyl acetate, vinyl methyl ether, and maleic anhydride, and an n-butyl ester, butyl acrylate, and acrylic. Examples thereof include a copolymer with an acid, cellulose, and acetate / hydrodiene phthalate.

The acidic polymer can be used as a mixture with a hydrophilic polymer. Examples of such hydrophilic polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether, and the like. Of these, polyvinyl alcohol is preferred.
Further, a polymer other than the hydrophilic polymer such as cellulose acetate may be mixed with the acidic polymer.

  The coating amount of the polymer acid is adjusted by the amount of alkali in the alkali treatment composition described later. The equivalent ratio of polymer acid to alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye changes or stains are produced in the white background, and if it is too much, problems such as a change in hue or a decrease in light resistance occur. 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 mass ratio of the hydrophilic polymer to the polymer acid is 0.01 to 10, preferably 0.1 to 3.0.

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

  In the present invention, the neutralization timing layer used in combination with the neutralization layer is, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, or the like. Polymers that lower alkali permeability; latex polymers that are made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer and that increase the activation energy of alkali permeation; polymers that have a lactone ring are useful.

  Of these, cellulose acetate disclosed in JP-A-54-136328, U.S. Pat. No. 4,267,262, U.S. Pat. No. 4,009,030, U.S. Pat. Timing layer: JP-A-54-128335, JP-A-56-69629, JP-A-57-6843, US Pat. Nos. 4,056,394, 4,061,496, 4,199, No. 362, No. 4,250,243, No. 4,256,827, No. 4,268,604, etc. are copolymerized with a small amount of a hydrophilic comonomer such as acrylic acid. Latex polymer prepared; polymer having monoacrylic acid ester or monomethacrylic acid ester of polyhydric alcohol disclosed in JP-A-11-2890 Polymers having a lactone ring disclosed in U.S. Pat. No. 4,229,516; other JP-A-56-25735, JP-A-56-97346, JP-A-57-6842, European Patent (EP) 31, The polymers disclosed in 957A1, 37,724A1, 48,412A1, etc. are particularly useful.

In addition, those described in the following documents can also be used.
U.S. Pat. Nos. 3,421,893, 3,455,686, 3,575,701, 3,778,265, 3,785,815, 3,847 No. 4,615, No. 4,088,493, No. 4,123,275, No. 4,148,653, No. 4,201,587, No. 4,288,523, No. 4,297,431, West German Patent Application (OLS) No. 1,622,936, No. 2,162,277, Research Disclosure 15162, no. 151 (1976). The neutralization timing layer using these materials can be used as a single layer or as a combination of two or more layers.

  Further, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, US Pat. 54-155837, 55-138745, etc., development inhibitors and / or precursors thereof, hydroquinone precursors disclosed in US Pat. No. 4,201,578, and other useful photographs. It is also possible to incorporate additives for use or precursors thereof. Furthermore, providing a neutralizing layer as described in JP-A Nos. 63-168648 and 63-168649 as the layer having the neutralizing function reduces the change in transfer density over time after processing. This is effective.

H) Others The cover sheet in the present invention may have a back layer, a protective layer, a filter dye layer, and the like as a layer having an auxiliary function in addition to the layer having a neutralizing function.
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 to prevent adhesion to the cover sheet back surface and adhesion to the photosensitive material protective layer when the photosensitive material and the cover sheet are overlapped. The sensitivity of the photosensitive layer can be adjusted by incorporating a dye into the cover sheet.
The filter dye may be added directly to the support of the cover sheet or the layer having a neutralizing function, and further to the back layer, protective layer, capture mordant layer, etc., or a single layer may be provided. .

III. Alkaline Processing Composition In the present invention, the alkali processing composition is uniformly spread on the photosensitive element after exposure of the photosensitive sheet (photosensitive element), and is (A) the back side of the support or the side opposite to the processing solution in the photosensitive layer. The photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed with the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light-shielding agent, a developer, a development accelerator for controlling development, a development inhibitor, and an antioxidant for preventing deterioration of the developer. Etc. A light-shielding agent is always included in the composition for light-shielding.

These alkali processing compositions are preferably developed on the photosensitive element with a development thickness (a processing liquid amount per m ² after transferring the processing liquid) of 10 μm to 200 μm. The processing temperature when processing the photosensitive element is preferably 0 to 50 ° C, more preferably 0 to 40 ° C.

  The alkali is sufficient to adjust the pH of the liquid to 12 or more, such as an alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide), an alkali metal phosphate (for example, potassium phosphate). , Guanidines and hydroxides of quaternary amines (for example, tetramethylammonium hydroxide), among which potassium hydroxide and sodium hydroxide are preferable.

  The thickener is necessary to uniformly develop the processing composition and to maintain adhesion between the photosensitive layer / cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose, or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or pigment or a combination thereof may be used as long as it does not diffuse to the dye image-receiving layer and produce stain. A typical example is carbon black.

  As the preferred developer, any developer can be used as long as it cross-oxidizes the dye image-forming compound and does not substantially produce stain even when oxidized. Such developing agents may be used alone or in combination of two or more, or may be used in the form of a precursor. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in the alkaline processing composition. Specific examples of the compound include aminophenols and pyrazolidinones. 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.

A development accelerator described in JP-A-62-215272, pages 72 to 91, a hardener described in pages 146 to 155, or a surfactant described in pages 201 to 210, in any one of a photosensitive sheet, a cover sheet and an alkali processing composition. A fluorine-containing compound described on pages 210-222, a thickener described on pages 225-227, an antistatic agent described on pages 227-230, a polymer latex described on pages 230-239, a matting agent described on page 240, and the like. Can do. Further, tertiary amine latexes described in JP-A-6-273907, JP-A-7-134386, JP-A-7-175193, and JP-A-7-287372 can be included.
The thickness of the diffusion transfer film unit of the present invention is not particularly limited.

  For 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 and heating method and apparatus to be applied, refer to, for example, [0128] to [0159] of JP-A-7-219180. 〕It is described in. A preferred exposure method is a method in which exposure is performed using an exposure head having different light sources that emit light in a plurality of specific wavelength regions.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.
Example 1

1. Preparation of photosensitive sheet First, photosensitive elements (photosensitive sheet-101) having the compositions shown in Tables 1 to 4 below were prepared. The emulsions in the table were prepared by the method shown in Table 5.

  The compounds used for the emulsion preparation are summarized below.

  The compound used for preparation of the photosensitive element (Photosensitive sheet-101) is shown below.

2. Production of Cover Sheet A polyethylene sheet having a thickness of 75 μm was coated on a transparent transparent support of polyethylene terephthalate to form a cover sheet 101 as shown in Table 6.

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

3. Production of Alkali Treatment Composition Next, an alkali treatment composition (treatment liquid-101) having the following composition was produced.
Carbon black (manufactured by Dainichi Seika Co., Ltd.) 224.3 g
Additive (23) 12.1 g
Carboxymethylcellulose Na salt 43.0 g
Potassium sulfite (anhydrous) 1.90 g
1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 13.6 g
Potassium hydroxide 52.7 g
Zinc nitrate 0.60g
Water was added in a total amount of 1 kg. 0.3 g of the treatment liquid having the above composition was filled into a container that could be broken by pressure.

  Next, the compound (I-10) represented by the general formula (I) and the compounds represented by the general formulas (II-1) to (II-4) (A-13) in the alkali treatment composition (101) ) Or (A-28) was added to prepare alkaline treatment compositions (102) to (110). In the same manner as the alkali treatment composition 101, these treatment compositions were filled in 0.3 g units in a container that can be broken by pressure.

  Using the photosensitive sheet-101, the cover sheet-101, and the processing solutions-101 to 109, color diffusion transfer photographic units -101 to 109 were prepared by a method such as JP-A-7-159931. After this color diffusion transfer photographic unit was loaded into the camera, it was exposed from the cover sheet side and developed with a pressure roller adjusted so that the processing liquid had a thickness of 55 μm between both materials. Exposure and development were performed. The treatment was performed at 25 ° C., and after 5 minutes from the development treatment, the reflection density after 1 day was measured with a color densitometer to obtain the maximum density and the minimum density.

The results are summarized in Table 7.
The present invention: When both the compound represented by the general formula (I) and the compounds represented by the general formulas (II-1) to (II-4) are used in combination, the minimum concentration is high although the maximum concentration is high. Was low and the transfer progressed quickly (105, 106).
Comparative example: When used alone, the fog was high, or the transfer progress was slow and the maximum density was low (101 to 104, 107 to 109).

Example 2
In the color diffusion transfer photographic unit production method of Example 1, the photosensitive element was changed to the photosensitive sheet-201, and a unit in which the developed thickness of the processing solution was changed was produced, and the effect was evaluated.

  First, photosensitive elements (photosensitive sheet-201) having the compositions shown in Tables 8 to 11 below were prepared.

  Three types of silver halide emulsions, surface latent image type emulsions-J, K, and L, were prepared and used according to the following preparation method. Table 12 summarizes the results.

Emulsion-K:
In 0.7 liter of gelatin aqueous solution containing 1.1 g of low molecular weight gelatin having 0.005 mol of potassium bromide and an average molecular weight of 20,000 or less, 26.5 ml of silver nitrate aqueous solution having a concentration of 0.58 mol / liter and 0.42 mol of potassium bromide 46.4 ml of an aqueous solution containing 1.5% by weight of a low molecular weight gelatin having an average molecular weight of 20,000 or less was mixed at the same time by virtue of the double jet method over 1 minute (first addition). During this period, the gelatin aqueous solution was kept at 35 ° C. After adding 0.5 g of potassium bromide, the temperature was raised to 75 ° C. with a gradient of 1.5 ° C. per minute.
After reaching a temperature of 75 ° C., 0.16 liters of gelatin solution containing 16% by mass of deionized gelatin having a Ca content of 100 ppm or less (first addition) and 5 ml of 4.9% sulfuric acid aqueous solution were added. Subsequently, a double jet at an accelerated flow rate (the flow rate at the end is 3.5 times the flow rate at the start) of a silver nitrate aqueous solution having a concentration of 1.88 mol / liter and a potassium bromide aqueous solution having a concentration of 1.88 mol / liter. (The second addition, the amount of silver nitrate aqueous solution used was 366 ml, and the amount of potassium bromide aqueous solution was 375 ml).

  Next, 0.08 liter of gelatin solution containing 14% by mass of deionized gelatin having a Ca content of 100 ppm or less (second addition) and 2 mg of sodium benzenethiosulfate were added. Subsequently, an aqueous solution of silver nitrate with a concentration of 1.88 mol / liter and an aqueous solution of potassium bromide with a concentration of 1.88 mol / liter are double jetted at an accelerated flow rate (the flow rate at the end is 1.2 times the flow rate at the start). (Added for the third time, the amount of silver nitrate aqueous solution used was 157 ml, and the amount of potassium bromide aqueous solution was 163 ml).

After adding 4.6 g of potassium bromide, it was washed with water by a conventional flocculation method, deionized gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added, and then adjusted to pH 5.8 and pAg 8.8. The emulsion was adjusted to contain 1.35 mol of silver and 84 g of gelatin per 1 kg of the emulsion. 0.74 kg of the emulsion thus prepared was dissolved by heating and heated to 55 ° C., then 0.5 g of potassium iodide, 4.2 × 10 ⁻⁴ mol of sensitizing dye (6), and sensitizing dye. 5.4 × 10 ⁻⁴ mol of (7) was added and aging was performed for 30 minutes. Next, 5.0 × 10 ⁻⁴ mol of potassium thiocyanate, 1.4 × 10 ⁻⁵ mol of potassium tetrachloroaurate, and 1.2 × 10 ⁻⁵ mol of sodium thiosulfate were added and aged for 60 minutes. Emulsion preparation was completed by adding 1.0 × 10 ⁻³ mol of Compound E-4 and further adding 3.2 × 10 ⁻⁴ mol of Compound E-5 at the end of ripening.

  The diameter of a circle having an area equal to the projected area when viewed from the main plane direction of each particle is called a circle equivalent diameter. As a result of observation by an electron microscope, the average value of the particle thickness hi (= Σhi × ni / Σni) was 0.135 μm, and the average value of the equivalent circle diameter Di of the particles (= ΣDi × ni / Σni) was 1.15 μm. The average aspect ratio defined by the average value of the equivalent circle diameter Di / the average value of the particle thickness hi was 8.5.

Emulsion-J:
Emulsion-J was prepared by adding 9.2 × 10 ⁻⁴ mol of sensitizing dye (9) instead of sensitizing dye (6) and sensitizing dye (7) in the preparation method of emulsion-K. .

Emulsion-L:
In the preparation method of Emulsion-K, sensitizing dye (1) is 8.4 × 10 ⁻⁴ mol instead of sensitizing dye (6) and sensitizing dye (7), and sensitizing dye (2) is 2.6. Emulsion-L was prepared by adding .times.10.sup.- ⁵ mol and sensitizing dye (3) to 1.7.times.10.sup.- ⁴ mol.

  The compounds used for the emulsion preparation are summarized below.

  Next, the compound (I-4), (I-10) or (I-11) represented by the general formula (I) and the general formulas (II-1) to (II-) are added to the alkali treatment composition (101). The compound (A-13), (A-28) or (A-29) represented by 4) was added to prepare alkaline treatment compositions (202) to (214). In the same manner as the alkali treatment composition 101, these treatment compositions were filled in 0.3 g units in a container that can be broken by pressure.

  Using the photosensitive sheet-201, the cover sheet-101, and the processing solutions-101, 202-214, color diffusion transfer photographic units-201-214 were produced by a method such as JP-A-7-159931. This color diffusion transfer photographic unit was subjected from exposure to development processing with an exposure development processing machine incorporating a three-color LED exposure machine of blue, green and red. After loading the color diffusion transfer photographic units -201 to 214 into the exposure development processing machine, the exposure is performed using the LED as a light source from the cover sheet side, and a pressure roller adjusted so that the processing liquid has a thickness of 38 μm between both materials. The unit-201 to 214 was exposed and developed. The treatment was performed at 25 ° C., and after 5 minutes from the development treatment, the reflection density after 1 day was measured with a color densitometer to obtain the maximum density and the minimum density.

The results are summarized in Table 13.
The present invention: When both the compound represented by the general formula (I) and the compounds represented by the general formulas (II-1) to (II-4) are used in combination, the minimum concentration is high although the maximum concentration is high. Was low and the progress of transcription was fast (205 to 209).
Comparative Example: When used alone, the fog was high, or the transfer progress was slow and the maximum density was low (201 to 204, 210 to 214).

Claims (5)

A photosensitive sheet having an image-receiving layer, a white reflective layer, a light-shielding layer, a silver halide emulsion layer combined with a dye image-forming substance on a transparent support, a transparent cover sheet having a neutralization layer and a neutralization timing layer on the support And a carbon black-containing alkali treatment composition developed between the photosensitive sheet and the transparent cover sheet, and a diffusion transfer film unit arranged so that these are exposed through the transparent cover sheet, the following general formula (I) At least one compound selected from the compounds represented by formula (II) and at least one compound selected from the group of compounds represented by the following general formulas (II-1) to (II-4): A diffusion transfer film unit, which is contained in a composition.

(In the formula, Q is an atomic group necessary for forming a 5-membered or 6-membered heterocyclic ring having at least one atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom as a constituent element) The nitrogen-containing heterocycle may have a substituent, but does not have a mercapto group as a substituent, and M is a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or an alkaline condition. A group that can be a hydrogen atom or an alkali metal atom is represented, and n represents 0 or 1.)

(In the formula, Q1, Q2, Q3, Q4 or Q5 may have a group of atoms or a substituent necessary for forming a 5-membered or 6-membered heterocyclic ring which may have a substituent. A group of atoms necessary for forming a 5- or 6-membered heterocyclic ring condensed with a benzene ring, wherein R1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl. Represents a group selected from the group consisting of groups, L represents a hydrogen atom or an alkali metal atom.)   The diffusion transfer film unit according to claim 1, wherein at least one compound selected from the group of compounds represented by formulas (II-1) to (II-4) is represented by formula (II-1). A diffusion transfer film unit characterized by being a compound to be produced.   3. The diffusion transfer film unit according to claim 1, wherein the silver halide emulsion in the diffusion transfer film unit photosensitive sheet is a negative type silver halide emulsion.   3. The diffusion transfer film unit according to claim 1, wherein the silver halide emulsion in the diffusion transfer film unit photosensitive sheet is an internal latent image type direct positive silver halide emulsion. . 5. The diffusion transfer film unit according to claim 1, wherein the diffusion transfer film unit is exposed using an exposure head having different light sources that emit light in a plurality of specific wavelength regions.