JP2604229B2 - Color Diffusion Transfer Photo Film Unit - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color diffusion transfer photographic film unit, and more particularly to a peelable color diffusion transfer photographic film unit.

(Prior Art) Conventional color diffusion transfer photographic film units are roughly classified into a peeling type and a peeling-free type. In the release type, the photosensitive layer and the dye image-receiving layer are provided on different supports, and after image exposure, the photosensitive element and the dye image-receiving element are superimposed, and the processing composition is developed during that time. By peeling off the element, a dye image transferred to the dye receiving layer is obtained.

The feature of this mode is that since the dye image formed on the image receiving layer coated on the support can be directly observed, there is no deterioration in image quality as seen in a peeling-free type described later, and a very excellent color It is to show the reproduction. On the other hand, there are inconveniences in the operation of superposing the photosensitive element and the image receiving element in the camera, and inconvenience in handling of the processed film that the alkaline processing solution is sticky after peeling and easily adheres to the periphery.

In order to solve such problems, Japanese Patent Application Laid-Open No. 63-226649 discloses at least (a) a layer having a neutralizing function, (b) a dye image receiving layer, (c) a release layer, and (d) a dye on a white support. A color diffusion transfer photographic film unit, comprising: a photosensitive element sequentially having at least one silver halide emulsion layer combined with an image forming substance; an alkaline processing composition comprising a sunscreen; and a transparent cover sheet. Japanese Patent Application No. 63-120201 (JP-A-1-289950) discloses that at least (a) a dye image-receiving layer, (b) a release layer,
(C) a photosensitive element having at least one silver halide emulsion layer sequentially combined with a dye image-forming substance, an alkaline processing composition containing a light-shielding agent, and having at least a neutralizing function on the side where the processing composition is developed. A color diffusion transfer photographic film unit comprising a transparent cover sheet having a layer is described, and a new type of peelable photographic film unit is proposed in each case. In addition, a dye image receiving layer and at least one silver halide emulsion layer combined with a dye image forming substance are provided on the same support, and a release layer is provided between the dye image receiving layer and the silver halide emulsion layer. U.S. Pat.Nos. 4,529,683, 4,499,174, 4,401,746, and 3,7 as peelable color diffusion transfer photographic film units having
Nos. 30,718 and 3,227,550.

(Problems to be Solved by the Invention) In a preferred embodiment of these peelable photographic film units, when the dye image-forming substance is a non-diffusible dye-releasing redox compound and a pyrazolidinone is used as a developing agent, stain occurs after peeling. Sometimes. It is desirable that the surface pH of the peeled surface immediately after peeling is preferably 10 or less, more preferably 8 or less. If the film unit does not have a neutralizing layer, of course, the film having a neutralizing layer may have a neutralizing layer. Even in the case of a unit, the surface pH of the peeled surface immediately after peeling may not be completely reduced. That is, when the pH is not sufficiently lowered due to peeling a little earlier than the desired peeling time, or when the pH gradually decreases after peeling, but immediately after peeling, it has not yet completely dropped. is there. On the peeled sheet surface including the dye image receiving layer peeled in a state where the pH has not been lowered in this way, there are cases where the developer is air-oxidized to produce pink stains or yellow-brown stains. The image quality was significantly impaired.

(Object of the Invention) It is an object of the present invention to provide a film unit having both a thin transfer color image print obtained by a peeling type color diffusion transfer photographic film unit and high image quality.

Another object of the present invention is to provide a peelable color diffusion transfer photographic film unit in which the occurrence of stain after peeling is suppressed.

(Means for Solving the Problems) As a result of intensive studies by the present inventors, A) a cover sheet including at least a layer having a neutralizing function on a transparent support, B)
An alkaline processing composition containing a light-blocking agent, C) at least sequentially on a support a) a dye image-receiving layer b) a release layer c) at least one silver halide emulsion layer combined with at least one dye image-forming substance And a color diffusion transfer photographic film unit including an image receiving photosensitive sheet containing a light-shielding agent on the opposite side of the alkali processing composition of the silver halide emulsion layer, wherein a sulfin film is provided between the support of the image receiving photosensitive sheet and the release layer. It has been found that this can be achieved by a color diffusion transfer photographic film unit characterized by containing a polymer having an acid group.

The polymer having sulfinic acid is preferably represented by the general formula [I].

General formula [I] R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-butyl group, and is preferably a hydrogen atom or a methyl group.

L represents a divalent linking group having 1 to 20 carbon atoms, for example, an alkylene group (eg, a methylene group, an ethylene group, a trimethylene group, a hexamethylene group, etc.), a phenylene group (eg, an o-phenylene group, a p-phenylene group) Group, m-phenylene group, etc.), arylenealkylene group (for example, Such. Here, R ² represents an alkylene group having 1 to 12 carbon atoms. _{), - CO 2 -, -} CO 2 -R 3 - ( where R ³ represents an alkylene group, phenylene group, an arylenealkylene ^{group), -. CONH-R 3} - ( where R ³ represents the same as above .), (However, R ¹ and R ³ represent those selected from the same group as described above.).

Particularly preferred as L is And so on.

Y represents a sulfinic acid group or a sulfinic acid group forming a salt. The cation forming the sulfinic acid group is 1
Trivalent to trivalent are preferred, and when they are divalent or more, the anion to be paired may contain other anions in addition to the monomer unit represented by the general formula [I].

Preferred cations include ammonium ions, metal ions and the like, and particularly preferred are alkali metal ions (eg, sodium ion and potassium ion).

Preferred specific examples of the monomer unit represented by the general formula (I) are shown below.

The polymer having a repeating unit having a sulfinic acid group of the present invention may contain a monomer unit obtained by copolymerizing another ethylenically unsaturated monomer in addition to the monomer unit represented by the general formula (I).

Examples of such ethylenically unsaturated monomers include:
Acrylic acid α-chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid), esters or amides derived from these acrylic acids (such as acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, -Methoxyethyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate , Ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate,
-Hydroxyethyl methacrylate, β-alkoxyethyl (meth) acrylate (eg, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate), vinyl ester (eg, vinyl acetate, vinyl laurate), acrylonitrile, methacrylonitrile,
Dienes (eg, butadiene, isoprene), aromatic vinyl compounds (eg, styrene, divinylbenzene and derivatives thereof, eg, vinyl toluene, vinyl acetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl Ether (for example, vinyl ethyl ether), N-vinyl-2-pyrrolidone, ethylene, propylene, 1-butene, isobutene and the like can be mentioned.

Of these, particularly preferred are acrylamide, N-
Vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, 2-methoxyethyl acrylate, methyl methacrylate, acrylonitrile and the like.

The ratio of the other ethylenically unsaturated monomers other than those represented by the general formula (I) can be changed arbitrarily.
It is preferably not more than 50 mol%, more preferably not more than 50 mol%.

The molecular weight of the polymer containing the repeating unit of the general formula [I] is preferably from 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too small, the polymer tends to move, and if the molecular weight is too large, coating may be hindered. Particularly preferred is 1 × 10 ⁴ to 2 × 10 ⁶ .

Preferred specific examples of the polymer containing a repeating unit represented by formula (II) used in the present invention are shown below.

 The composition ratios are all molar ratios.

The use of polymers having sulfinic acid groups in color diffusion transfer photographic film units is disclosed in
No. 5,538,845 discloses that the storage stability of the alkali processing composition is improved by being contained in the alkali processing composition, and a method of hardening gelatin in combination with a gelatin hardener in a photographic light-sensitive material is disclosed. JP-A-56-41
41. The former is completely different from the present invention in the position and effect of addition, and the latter is for hardening gelatin, and is clearly different from the effect of the present invention. Preferred embodiments of including the polymer in gelatin in the present invention are included in the range of the above-mentioned JP-A-56-4141, but the above-mentioned patent includes not only the constitution as in the present invention but also the specific structure in the present invention. No effect is shown. Therefore, the present invention can be said to be a completely new and unexpected effect.

The effect of the present invention is that a photosensitive layer and an image receiving layer are coated on a separate support, as shown in JP-B-49-26896, of a peelable color diffusion transfer photographic film unit. And an image-receiving element, and the processing composition is developed between them. Thereafter, the image-receiving element is peeled off to obtain a dye image transferred to the image receiving layer.
The photosensitive layer and the image receiving layer as shown in No. 226649 are coated on the same support, and after image exposure, the processing composition is developed between the cover sheet and the photosensitive layer and the image receiving layer. Peeling the image receiving layer through the release layer, it is also recognized in a type that can directly observe the image without the support, U.S. Pat.No.4,499,174, the photosensitive layer and the image receiving layer as shown in the same 4,529,683 Coated on the same support, after image exposure,
A type in which a processing composition is developed between a cover sheet and a type in which an image is observed by peeling off an image receiving layer via a release layer between a photosensitive layer and an image receiving layer and then as shown in Japanese Patent Application No. 63-120201. On a white support, at least (a) a dye image-receiving layer,
(B) a release layer, (c) a photosensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming substance, an alkali treatment composition containing a light-shielding agent, and a transparent cover sheet having a neutralizing function. This is particularly noticeable in the type in which the neutralizing layer does not remain on the sheet containing the peeled dye image-receiving layer, such as the type consisting of Japanese Patent Application No. 63-120201.
The type described in the item is highly effective because it is highly likely that it will be peeled off before the pH is not sufficiently lowered.

In the present invention, the position where the polymer represented by the general formula [I] is added is not particularly limited as long as it is a layer between the support of the image receiving photosensitive sheet and the release layer, but a layer close to the surface after release is preferable. However, when a quaternary ammonium salt type polymer is used as a mordant in the image receiving layer as described later, the quaternary ammonium salt polymer and the sulfinic acid group-containing polymer are aggregated, and it is difficult to add them. In these cases as well, if necessary, another layer may be provided above or below the image-receiving layer to contain a polymer having a sulfinic acid group. Of course, it can be contained in another layer, for example, an auxiliary layer such as an adhesion improving layer, an ultraviolet absorbing layer, or a protective layer. If necessary, it may be distributed and contained in several layers.

The amount of the polymer having sulfinic acid to be contained in the present invention varies depending on the position to be contained, the type of polymer, the type of binder used, and the like, and cannot be unconditionally determined, but is 0.1 to 50 mmol / m ^{2 in the} sulfinic acid unit. Preferably it is 0.5 to 20 mmol / m ^{2, more} preferably 1 to 10 mmol / m ² .

The binder used in combination with the polymer having a sulfinic acid group in the present invention is not particularly limited as long as it is hydrophilic and can be mixed with the polymer in the present invention. Generally, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone Etc. are used, but gelatin is preferred.

 Hereinafter, each of these components will be described.

A) Support for photosensitive element The support used in the present invention is a transparent support, a white support, a black support or the like which is usually used as a smooth photographic support. As a transparent support, polyethylene terephthalate having a thickness of 50 to 350 μm, preferably 70 to 210 μm,
Cellulose acetate, polycarbonate and the like are used. The transparent support may contain a minute amount of a pigment such as titanium dioxide or a small amount of a dye to prevent light piping.

The preferred white support in the present invention refers to a support in which at least the side on which the dye image-receiving layer is coated is white, and any support having sufficient whiteness and smoothness can be used. For example, a polymer film whitened by addition of a white pigment such as titanium oxide, barium sulfate, zinc oxide or the like having a particle size of 0.1 to 5 μm and formation of microvoids by stretching, for example, polyethylene terephthalate formed by sequential second axial stretching in a conventional manner , A film made of polystyrene or polypropylene, a synthetic paper, or a paper obtained by laminating polyethylene, polyethylene terephthalate, polypropylene or the like containing titanium white on both sides of the paper is preferably used.

The thickness of the support is 50-350 μm, preferably 70-210 μm
m, more preferably 80-150 μm. If necessary, a light-shielding layer may be provided in the support.
For example, a support obtained by laminating polyethylene containing a light-shielding agent such as carbon black on the back surface of a white support is used.

As the black support, a thickness of 50 to 350 μm, preferably 70 to 210 μm containing a light-shielding agent such as carbon black, polyethylene terephthalate, cellulose acetate, polycarbonate, polystyrene, polypropylene, etc.
Or a thickness of 50 including a light-blocking agent such as carbon black
A laminate obtained by laminating polyethylene, polyethylene terephthalate, polypropylene or the like on both sides of a paper support having a thickness of from 400 to 400 μm, preferably from 70 to 250 μm, is preferably used.

Examples of carbon black raw materials include Donnel Voet
Any method such as a channel method, a thermal method and a furnace method described in "Carbon Black" Marcel Dekker, Inc. (1976) 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 shaded,
An optical density of about 5 to 10 is desirable.

When a black support is used or when the whiteness of a white support is insufficient, it is necessary to provide a white light reflective layer between the support and the dye image-receiving layer. , Barium sulfate, white pigments such as zinc oxide,
It is preferred to provide a layer containing a hollow polymer latex.

In the present invention, it is preferable to use a white support, and particularly preferable is a polyethylene terephthalate white support containing titanium oxide.

B) Dye image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This is a single layer,
Further, it may have a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-252551. As the mordant, a polymer mordant is preferable.

The polymer mordant used in the present invention is a polymer having a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, and a polymer having a molecular weight of 5,000 or more, particularly preferably 10,000. That's all.

For example, U.S. Pat.Nos. 2,548,564, 2,484,430, 3,
148,061, 3,756,814, etc .; vinylpyridine polymer and vinylpyridinium cationic polymer; U.S. Pat.No. 4,124,386, vinylimidazolium cationic polymer disclosed in U.S. Pat.No. 3,625,694, 3,859,096 U.S. Pat. No. 3,958,995; U.S. Pat. No. 3,958,995;
No. 2,721,852, No. 2,798,063, JP-A-54,115,228,
No. 54-145,529, No. 52-126,027, No. 54-155,835
Aqueous sol-type mordants disclosed in U.S. Pat. Nos. 5,17,352; and the like; water-insoluble mordants disclosed in U.S. Patent 3,898,088, and the like; U.S. Patents 4,168,976 and 4,201,8
Reactive mordant capable of forming a covalent bond with the dye disclosed in the specification of JP-A No. 40,038 / 1990; and US Pat. Nos. 3,709,690 and 3,788,8
No. 55, No. 3,642,482, No. 3,488,706, No. 3,557,
No. 066, No. 3,271,147, No. 3,271,148, JP 53
-30328, 52-155528, 53-125, 53-1024
No. 53-107,835 and British Patent 2,064,802.

Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

Among these mordants, those that are difficult to move from the mordant layer to the other layer are preferable, and those that undergo a crosslinking reaction with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants are preferable. . Particularly preferred is a latex dispersion mordant, having a particle size of 0.01 to
2μ, preferably 0.05-0.2μ.

The coated amount of the mordant, the type of mordant, the content of quaternary cationic groups, dye type and amount to be mordanted, different but 0.5 to 10 g / m ^2, preferably by the like binder species used connexion 1.0 to 5.
0 g / m ^2, particularly preferably 2 to 4 g / m ^2.

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable.

C) Light-shielding layer In the present invention, the light-shielding layer in the photosensitive element and the light-shielding processing solution developed on the photosensitive element during processing completely shield the photosensitive layer from external light during the development processing. , Enabling processing under daylight. Specifically, a layer containing a light-blocking agent may be coated on the back surface of the support or between the emulsion layer and the support, or a layer containing a light-blocking agent may be provided in the support. As the light-shielding agent, any material having a light-shielding function can be used, but carbon black is preferably used.

The binder for applying the light-shielding agent may be any binder capable of dispersing the carbon black, and is preferably gelatin.

D) Release Layer In the present invention, a release layer is provided between the emulsion layer combined with the dye image-forming substance and the dye image-receiving layer, and the emulsion layer is peeled off after the processing. Therefore, the release layer must maintain adhesion between the image receiving layer and the emulsion layer in an unprocessed state, and must be easily peelable after processing. As the material for this, for example, JP-A-47-8237, JP-A-59-220727, JP-A-59-229555,
No. 49-4654, U.S. Pat.
4334, 56-65133, 45-24075, U.S. Pat.
Those described in 2759825, 4401746, 4366227 and the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. For example, 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.
Still another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, butyl methacrylate, or a copolymer thereof.

The release layer may be a single layer or a plurality of layers, and is described in, for example, JP-A-59-220727 and JP-A-60-60642.

As an example of a release layer particularly suitable for the present invention, Japanese Patent Application No.
-23493, 63-155934, 63-76859, 63-22
Nos. 526, 63-76860 and 63-76861.

E) Photosensitive layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image-forming substance is provided above the release layer. The components are described below.

(1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or has a diffusivity of itself. Is changing, and the theory of the photographic process “The Theo”
ry of the Photographic Process ", 4th edition. All of these compounds can be represented by the following general formula (I).

DYE-Y (I) Here, DYE represents a dye or a precursor thereof, and Y represents a component which gives a compound having a different diffusibility from the compound under alkaline conditions. According to the function of Y, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion.

Particularly preferably, it is a non-diffusible dye-releasing redox compound, particularly preferably itself a non-diffusible negative dye-releasing redox compound.

Specific examples of the negative type Y include those which oxidize as a result of development and are cleaved to release a diffusible dye.

Specific examples of Y are U.S. Patents 3,928,312, 3,993,638,
No. 4,076,529, No. 4,152,153, No. 4,055,428, No. 4,0
No.53,312, No.4,198,235, No.4,179,291, No.4,149,89
No. 2, 3,844,785, 3,443,943, 3,751,406,
3,443,939, 3,443,940, 3,628,952, 3,9
80,479, 4,183,753, 4,142,891, 4,278,75
No. 0, 4,139,379, 4,218,368, 3,421,964,
4,199,355, 4,199,354, 4,135,929, 4,3
No. 36,322, 4,139,389, JP-A-53-50736, 51-
No. 104343, No. 54-130122, No. 53-110827, No. 56-12
No. 642, No. 56-16131, No. 57-4043, No. 57-650,
Nos. 57-20735, 53-69033, 54-130927, 56
Nos. 164342 and 57-119345.

Among the Y's in the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). The representative groups of Y are illustrated below, but are not limited thereto.

For positive-type compounds, see Angevante Hemi International Edition English.
v. Chem. Inst. Ed. Engl), 22, 191 (1982).

As a specific example, a diffusible dye is released by, for example, self-ring closure under alkaline conditions, but the dye is not substantially released when oxidized during development. Specific examples of Y having such a function are described in U.S. Pat. No. 3,980,479, JP-A-53-69033 and JP-A-54-130927, U.S. Pat. Nos. 3,421,964 and 4,199,355.

Another type does not release the dye itself, but releases the dye when reduced. Compounds of this type can be used in combination with an electron donor to release imagewise diffusible dyes by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, for example, U.S. Pat.
183,753, 4,142,891, 4,278,750, 4,139,379,
4,218,368, JP-A-53-110827, U.S. Pat.
4,356,249, 4,358,525, JP-A-53-110827, 54-13
0927, 56-164342, Published Technical Report 87-6199, European Patent Publication
It is described in 220746A2 and the like.

Specific examples will be described below, but the present invention is not limited thereto.

When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or a precursor thereof. ED
Examples of compounds include, for example, U.S. Pat.
78,750 and JP-A-56-138736.

On the other hand, specific examples of the dye represented by DYE in the above general formula are described in the following documents.

Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, and 4,013,633
Nos. 4,245,028, 4,156,609, 4,139,383,
4,195,992, 4,148,641, 4,148,643, 4,3
No. 36,322: JP-A-51-114930, JP-A-56-71072: Resear
ch Disclosure 17630 (1978) and 16475 (1977).

Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380
No. 3,931,144, No. 3,932,308, No. 3,954,476,
4,233,237, 4,255,509, 4,250,246, 4,1
42,891, 4,207,104 and 4,287,292: JP-A-52-292
No. 106,727, No. 52-106727, No. 53-23,628, No. 55-3
6,804, 56-73,057, 56-71060, 55-134
What is described in the issue.

Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635
No. 4,268,625, No. 4,171,220, No. 4,242,435,
No. 4,142,891, No. 4,195,994, No. 4,147,544, No. 4,1
48,642; British Patent 1,551,138; JP-A-54-99431;
No. 52-8827, No. 53-47823, No. 53-143323, No. 54
-99431, 56-71061; European Patent (EPC) 53,
No. 037, 53,040; Research Disclosure 17,630 (1978)
And those described in No. 16,475 (1977).

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

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, and metal ions doped or chemically sensitized, or both. "Core / shell type" emulsions in which at least the photosensitive sites of the silver halide inner core (core) grains are coated with an outer shell (shell) of silver halide. ,twenty five
0, 3,206,313, UK Patent 1,027,146: U.S. Patent 3,761,27
6, 3,935,014, 3,447,927, 2,497,875, 2,563,
785, 3,551,662, 4,395,478, West German patent 2,728,108,
It is described in U.S. Pat. No. 4,431,730.

When an internal latent image type direct positive emulsion is used, it is necessary to give fog nuclei on the surface by using light or a nucleating agent after image exposure.

U.S. Patent Nos. 2,563,785 and
Hydrazines described in 2,588,982, U.S. Pat.
Hydrazides and hydrazones described in 52, UK patent
1,283,835, JP-A-52-69613, U.S. Pat.
Heterocyclic quaternary salt compounds described in 3,719,494, 3,734,738, 4,094,683, 4,115,122, etc., U.S. Pat.
Described in, a sensitizing dye having a substituent having a nucleating effect in the dye molecule, U.S. Patent Nos. 4,030,925, 4,031,127, and 4,
245,037, 4,255,511, 4,266,013, 4,276,364, thiourea-bonded acylhydrazine-based compounds described in British Patent 2,012,443 and the like, and U.S. Pat.Nos. 4,080,270 and 4,27
For example, an acylhydrazine-based compound having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorptive group described in U.S. Pat.

In the present invention, a spectral sensitizing dye is used in combination with the negative emulsion and the internal latent image type direct positive emulsion. Specific examples thereof are described in JP-A-59-180550 and JP-A-60-140335, Research Disclosure (RD) 17029, U.S. Pat.
6,300, 2,078,233, 2,089,129, 2,165,338, 2,
231,658, 2,917,516, 3,352,857, 3,411,916,
2,295,276, 2,481,698, 2,688,545, 2,921,067,
3,282,933, 3,397,060, 3,660,103, 3,335,01
0, 3,352,680, 3,384,486, 3,623,881, 3,718,
470, and 4,025,349.

(3) Composition of photosensitive layer To reproduce a natural color by a subtractive color method, the dye image-forming substance which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye. And a photosensitive layer composed of at least two of the following combinations. The emulsion and the dye image forming substance 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 substance 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, and JP-A-60-91354 discloses The reflective layer described above can be provided to enhance the sensitivity of the photosensitive element.

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.

When a developing agent is used in combination with the non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the oxidized form of the present development. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, and sulfonamide naphthol. More specifically, Japanese Patent Publication Nos. 50-21249 and 50-23813, and JP-A-49-10
6329, 49-129535, U.S. Patents 2,336,327, 2,360,29
0, 2,403,721, 2,544,640, 2,732,300, 2,782,
659, 2,937,086, 3,637,393, 3,700,453, British Patent 557,750, JP-A-57-24941, and JP-A-58-21249. The dispersing method is described in JP-A-60-23.
8831, and JP-B-60-18978.

In the present invention, an anti-irradiation layer, an isolating layer, a protective layer and the like are provided as needed.

F) 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 surface 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. In the meantime, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. For this purpose, the composition contains an alkali, a thickening agent, a light-blocking agent, a developer, and further, a development accelerator for controlling development, an antioxidant for preventing deterioration of the developer, and the like. It contains. The composition always contains a light-shielding agent.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide) and alkali metal phosphates (eg, potassium phosphate). , Guanidines,
Examples include quaternary amine hydroxides (eg, tetramethylammonium hydroxide, etc.), and among them, potassium hydroxide and sodium hydroxide are preferable.

The thickener is necessary to spread the processing solution uniformly, and to maintain the close contact between the photosensitive layer and the cover sheet when the used photosensitive layer is peeled off together with 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 a carbon black, but a combination of titanium white and a dye is also used. The dye may be a temporary light-shielding dye that becomes colorless after a certain period of processing.

Preferred developers cross-oxidize the dye image-forming substance,
Any material can be used as long as it 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 element, or may be contained in an alkaline processing solution. Specific compounds include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferred.

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.

After processing, the cover sheet is peeled off and discarded together with the processing solution and the used photosensitive layer. However, the cover sheet has a function of uniformly spreading the processing solution on the photosensitive element and neutralizing the alkali introduced from the processing composition.

The sensitivity of the photosensitive layer can be adjusted by adding a filter dye to the cover sheet. The filter dye may be added directly to the support of the cover sheet, or may be applied as a separate layer.

G) Cover sheet support The support used for the cover sheet of the present invention is a transparent support which is smooth and is usually used as a photographic support. Preferably 50-350 μm in thickness, preferably 50-210 μm
Polyethylene terephthalate, cellulose acetate, polystyrene, polycarbonate and the like. The transparent support preferably contains a minute amount of a dye or a minute amount of a pigment such as titanium dioxide in order to prevent light piping. The transparent support is preferably provided with an undercoat layer.

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 carried in from the treatment composition, and if necessary, It may have a multilayer structure composed of layers such as a neutralization rate adjusting layer (timing layer) and an adhesion reinforcing layer. Preferred acidic substances are substances containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis), and more preferably oleic acid described in U.S. Pat. No. 2,983,606. Higher fatty acids such as polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 3,362,819; acrylics as disclosed in French Patent 2,290,699 Acid and acrylate copolymers; U.S. Pat. No. 4,139,383 and Research Disclosure N
o. 16102 (1977).

Others, U.S. Pat.No. 4,088,493, JP-A-52-153,739
No. 53-1,023, No. 53-4,540, No. 53-4,541,
The acidic substances disclosed in JP-A-53-4,542 and the like can also be mentioned.

Specific examples of the acidic polymer include a copolymer of ethylene, vinyl acetate, a vinyl monomer such as vinyl methyl ether, and maleic anhydride and its n-butyl ester,
Copolymers of butyl acrylate and acrylic acid, cellulose acetate hydrogendiphthalate, and the like.

The polymer acid may be used alone or in combination with a hydrophilic polymer. Examples of such a polymer 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, such as cellulose acetate, may be mixed with the polymer acid.

The amount of the polymer acid applied is adjusted by the amount of the 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 changes, or a stain occurs on a white background, and the hue changes even when the amount is too large.
Otherwise, inconveniences such as a decrease in light resistance occur. A more preferred equivalent ratio is 1.0-1.3. When mixed with a hydrophilic polymer, the amount of the hydrophilic polymer is too large or too small, and the quality of the photograph is deteriorated. The weight ratio of hydrophilic polymer to polymeric acid is 0.1-10, preferably 0.3-3.0.

Additives can be incorporated into the layer having a neutralizing function of the present invention 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. In addition, if necessary, an antioxidant, a development inhibitor and a precursor thereof can be added.

Timing layers used in combination with the neutralizing layer include polymers that reduce alkali permeability such as, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like; A latex polymer made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer to increase the activation energy of alkali permeation;
A polymer having a lactone ring is useful.

Among them, JP-A-54-136328, U.S. Pat.
No. 4,009,030, 4,029,049, etc .; Timing Layer Using Cellulose Acetate;
Nos. 8335, 56-69,629, 57-6,843, U.S. Pat.
Nos. 56,394, 4,061,496, 4,199,362, 4,250,24
Nos. 4,229,51 and 4,256,827, and 4,268,604, etc., a latex polymer produced by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid;
A polymer having a lactone ring disclosed in JP-A-6-25735, JP-A-56-97346, JP-A-57-6842, and European Patents (EP) 31,957A1, 37,724A1, 48. Four
The polymers disclosed in, for example, No. 12A1, are particularly useful.

 In addition, those described in the following documents can also be used.

U.S. Patent Nos. 3,421,893, 3,455,686, 3,575,701
Nos. 3,778,265, 3,785,815, 3,847,615,
4,088,493, 4,123,275, 4,148,653, 4,2
01,587, 4,288,523, 4,297,431, West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disc
losure15,162 No.151 (1976).

As the neutralization timing layer for taking the reverse S-shaped pH lowering process, an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (eg, acrylic acid, methacrylic acid, itaconic acid) is used. Copolymers of one or more kinds,
Nos. 4,029,086, and polymers such as those described in U.S. Pat.
7,431, 4,288,523, 4,201,587, 4,229,516
Nos., JP-A-55-121438, JP-A-56-166212, and JP-A-55-4149.
0, 55-54341, 56-102852, 57-141644
No. 57-173834, No. 57-179841, West German Patent Application Publication (OLS) 2,910,271, European Patent Application Publication EP31957A1, R
esearch Disclosure No. 18452 and the like. As the ethylenically unsaturated monomer, for example, ethylene, propylene, 1-butene, isobutene,
Styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N, N, N-trimethyl-N-vinylbenzylammonium chloride, N, N-dimethyl-
N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, 1-vinyl-2- Methyl imidazole, monoethylenically unsaturated esters of aliphatic acids (eg, vinyl acetate, allyl acetate), maleic anhydride, ethylenically unsaturated esters of monocarboxylic or dicarboxylic acids (eg, n-butyl acrylate, n-hexyl acrylate) , Hydroxyethyl acrylate, cyanoethyl acrylate, N, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl Methacrylate, methoxyethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N, N-triethyl -N- methacryloyloxyethyl ammonium p- toluenesulfonate,
N, N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconate, monobenzyl maleate),
Amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg acrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, N-
(N, N-dimethylaminopropyl) acrylamide, N,
N, N-trimethyl-N- (N-acryloylpropyl)
Ammonium-p-toluenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, acryloylmorpholine, methacrylamide, N, N-dimethyl-N'-acryloylpropanediaminepropionate betaine, N, N-dimethyl-N '-Methacryloylpropanediamine acetate betaine) and the like.

 The neutralization timing layer may be a single layer or multiple layers.

In addition, for example, US Pat. No. 4,009,029 and West German Patent Application (OLS) 2,913,164
No. 3,014,672, JP-A-54-155837, and 55-13874
No. 5, etc., and a development inhibitor disclosed therein and / or a precursor thereof, or a hydroquinone precursor disclosed in U.S. Pat. No. 4,201,578, and other photographic useful additives or precursors thereof can also be incorporated. .

The film unit of the present invention is disclosed in JP-B-48-33697, JP-A-48-43317, JP-A-50-153628, JP-A-52-11027, and JP-A-56-4862.
In the same manner as described in 9, it is processed into a monosheet using a masking agent, a rail material, a surplus liquid trap material, and the like.

In particular, Research Disclosure No. 23026 to facilitate peeling after processing
It is effective to add a slit as described in (1983). The shape and depth of the slit are selected according to the physical properties of the support used.

(Examples) Example-1 Image-Received Photosensitive Sheet I The following layers (A), (B) and (C) were formed on the back of a PET support containing a titanium white white pigment, and the following layers (1) to (C) were formed on the opposite side.
(22) An image receiving photosensitive sheet I was prepared by coating the layer.

(A) Carbon black 2.0 g / m ² and gelatin 2.0 g / m ²
And a light-shielding layer.

(B) a white layer containing titanium white 2.0 g / m ² and gelatin 0.7 g / m ^2.

(C) Polymethyl methacrylate spherical matting agent 0.09 g /
protective layer comprising m ² and gelatin 0.3 g / m ^2.

(1) below the polymer latexes mordant 3 g / m ² and gelatin 3 g / m ² comprises a mordant layer.

(2) A first release layer comprising the following compound 0.1 g / m ² .

(3) A second release layer composed of 0.2 g / m ² of cellulose acetate having a degree of oxidation of 51%.

(4) Ethyl acrylate lattes try 1 g / m ² gelatin 2.5 g / m ² comprises the layer.

(5) The following cyan dye releasing redox compound 0.44 g /
m ^2, tricyclohexyl phosphine benzoate 0.09g / m ^2, 2,5-
Di -t- pentadecylhydroquinone 0.008 g / m ^2, the layer containing carbon black 0.05 g / m ^2, and gelatin 0.8 g / m ^2.

(6) A light reflection layer containing ² g / m ² of titanium oxide and 0.5 g / m ² of gelatin.

(7) Octahedral internal latent image type direct positive silver bromide emulsion having a grain size of 1.0 μm (silver amount: 0.15 g / m ² ) Red-sensitive sensitizing dye, gelatin: 0.4 g / m ² , nucleation: Low-sensitivity red-sensitive emulsion layer containing 1.1 μg / m ^{2 of} Agent (NA) and 0.02 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

NA (8) An internal latent image type direct positive silver bromide emulsion having a grain size of 1.6 μm octahedron (0.5 g / m ^{2 in} silver) Same as the following red-sensitive sensitizing dye, gelatin 0.8 g / m ² layer (7) Nucleator (NA) 3.0μ
A high-sensitivity red-sensitive emulsion layer containing g / m ² and 0.04 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

Red-sensitive sensitizing dye (9) 2,5-di-t-pentadecylhydroquinone 1.2
An anti-color mixing layer containing g / m ² , 1.2 g / m ² of polymethyl methacrylate and 0.7 g / m ² of gelatin.

(10) A layer containing 0.3 g / m ² of gelatin.

(11) The following magenta dye-releasing redox compound 0.15
g / m ^2, tricyclohexyl phosphine benzoate 0.1g / m ^2, 2,5-
Di -t- pentadecylhydroquinone 0.009 g / m ² and gelatin 0.9 g / m ² containing layers.

(12) titanium oxide 1 g / m ² and the light reflective layer containing gelatin 0.25 g / m ^2.

(13) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.0 μm (0.12 g / m ^{2 in} silver), green sensitizing dye below, gelatin 0.25 g / m ² , layer (7) Same nucleating agent (NA) 1.
A low-sensitivity green-sensitive emulsion layer containing 1 μg / m ² and 0.02 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

(14) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (silver amount 0.35 g / m ² ) The following green-sensitive sensitizing dye, gelatin 0.7 g / m ² , layer (7) The same nucleating agent (NA) 1.7
Highly sensitive green-sensitive emulsion layer containing μg / m ² and 0.04 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

Green-sensitive sensitizing dye and (15) 2,5-di-t-pentadecylhydroquinone 0.8
g / m ^2, polymethyl methacrylate 0.8 g / m ² and color mixing prevention layer containing gelatin 0.45 g / m ^2.

(16) A layer containing 0.3 g / m ² of gelatin.

(17) A yellow dye-releasing redox compound (0.53 g / m ² ) having the following structure, tridiclohexyl phosphate (0.13 g / m ² )
g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014g / m ²⁾ and a layer containing gelatin (0.7g / m ^2).

(18) Titanium oxide 0.7 g / m ² and the light reflective layer containing gelatin 0.18 g / m ^2.

(19) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.1 μm (silver amount: 0.25 g / m ² ) The following blue-sensitive sensitizing dye, gelatin: 0.4 g / m ² , layer (7) Same nucleating agent (NA) 2 as
A low-sensitivity blue-sensitive emulsion layer containing μg / m ² and 0.045 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

(20) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.7 μm (0.42 g / m ^{2 in} silver), the following blue-sensitive sensitizing dye, gelatin 0.45 g / m ² , layer (7) Same nucleating agent (NA) 3.
A high-sensitivity blue-sensitive emulsion layer containing 3 μg / m ² and 0.025 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt.

Blue-sensitive sensitizing dye (21) Each of the following UV absorbers is 4 × 10 ^-4 mol
/ m ² , and an ultraviolet absorbing layer containing 0.5 g / m ² of gelatin.

(22) A protective layer containing matt and gelatin at 1.0 g / m ² .

Image receiving photosensitive sheets II to IV Image receiving photosensitive sheets II to IV were prepared in exactly the same manner as image receiving photosensitive sheet I except that the following layers were applied under layer (1) (on the support side) of image receiving photosensitive sheet I.

Receiving photosensitive sheet II: Gelatin 1.5 g / m ² layer receiving photosensitive comprises a sheet III: Gelatin 1.5 g / m ² and polystyrenesulfonic fins potassium to 0.56 g / m ² comprising a layer receiving photosensitive sheet IV: Gelatin 1.5 g / m ² And layers containing 0.93 g / m ^{2 of} potassium polystyrene sulfinate. Image-receiving photosensitive sheets V to VIII except that the following layers were applied between layers (1) and (2) of the image-receiving photosensitive sheets. Exactly similar image-receiving photosensitive sheets V to VII were produced.

Receiving photosensitive sheet V: Gelatin 0.5 g / m layer receiving photosensitive including ² Sheet VI: Gelatin 0.5 g / m ² and polystyrenesulfonic fins potassium 0.38 g / m ² comprising a layer receiving photosensitive sheet VII: Gelatin 0.5 g / m ² and polystyrenesulfonic Huynh potassium 0.56 g / m ² comprising a layer receiving photosensitive sheet VIII: gelatin 0.5 g / m ² and exemplary compound (8) 0.51 g / m ² comprises the layer.

Cover Sheet As a cover sheet, the following layers (1) and (2) were provided on a polyethylene terephthalate transparent support containing a gelatin-primed anti-light-piving dye.

(1) Acrylic acid-butyl acrylate (average molecular weight: 8: 2) copolymer having an average molecular weight of 50,000 was 10.4 g / m ² and 1,4-bis (2,3-epoxypropoxy) -butane 0.1 g / m ^2. Neutralizing layer containing.

(2) the following polymer 2.9 g / m ^2, poly (methyl vinyl ether - co - monobutyl maleate) 0.29 g / m ² neutralization timing layer containing.

The image receiving photosensitive sheet is exposed to light through a color test chart, superimposed on the cover sheet, and the following processing solution is developed between the two sheets so as to have a thickness of 75 μm (development is performed with the aid of a pressure roller. Was).

The treatment was performed at 25 ° C., and peeling was performed at 2 minutes 30 seconds and 10 minutes after the treatment.

Peeling occurred in the peeling layer in the photosensitive sheet, and a color image was directly observed.

Processing liquid 25 ° C after peeling samples peeled at each peeling time
After leaving for 2 hours under the condition of 70% RH, measurement was carried out with a TCD concentration measuring device manufactured by Fuji Photo Film Co., Ltd. Table 1 summarizes the highest transfer density and the lowest density.

B, G, and R are transfer densities measured with blue, green, and red filters, respectively.

As shown in Table 1, when the polymer of the present invention is contained, the peeled print gradually develops a pink color and becomes stained when peeled in a relatively short time without causing a decrease in the maximum transfer density. (Represented by the lowest density in the G filter), and it can be seen that reflective prints of excellent image quality are provided.

Claims (1)

(57) [Claims] 1. A cover sheet comprising at least a layer having a neutralizing function on a transparent support, B) an alkali treatment composition containing a light-shielding agent, C) at least sequentially on a support, a) a dye image-receiving layer, b) release. Layer c) An image-receiving light-sensitive sheet comprising at least one silver halide emulsion layer in combination with at least one dye image-forming substance, and comprising a light-shielding agent on the opposite side of the silver halide emulsion layer from the alkaline processing composition. A color diffusion transfer photographic film unit comprising a polymer having a sulfinic acid group between a support of the image receiving photosensitive sheet and a release layer.