JPS5933895B2 - photo elements - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photographic elements, and more particularly to photographic elements for color diffusion transfer processes.

The greatest feature of color diffusion transfer photographic materials is that they are developed and can be viewed immediately after being photographed.Due to their nature, the developing conditions, particularly the processing temperature, may vary depending on the location where the photograph was taken and the photographing temperature. It is directly affected by the temperature at that time of year.

However, it is almost impossible to control the temperature at the location and time of photography to the appropriate temperature for development processing, so various measures have been taken to provide excellent color images even if the shooting and processing temperatures fluctuate. is being done. U.S. Patent No. 400902 by Hammond et al. to suppress excessive and unnecessary development at high temperatures.
No. 9 describes the use of a new development inhibitor precursor, and describes that by adding it to the cover sheet of a photographic element for color diffusion transfer, the range of acceptable processing temperatures on the high-temperature side can be expanded. Furthermore, in order to compensate for the lack of development and the delay in diffusion transfer, especially at low temperatures, Hannie
According to West German patent application (OLS) No. 2716505 by
A method is disclosed to extend the processing temperature tolerance range by using a neutralized timing layer obtained with latex of 1/mol.

Further, in the examples of the West German patent application (OLS) No. 2716505, the aforementioned development inhibitor precursor 5-(2
-cyanoethylthio)-1 layer phenyltetrazole and the activation energy of penetration of alkaline treatment liquid are 18Kca
There is a description that by using a neutralized timing layer obtained from latex in an amount of 1/mol or more, it is possible to expand the processing temperature tolerance range to both the low temperature side and the high temperature side.

However, although the photosensitive material using the five-layer (2-cyanoethylthio)-one-layer phenyltetrazole and the neutralization timing layer has a wider processing temperature range, the color image density decreases as time passes after processing. This results in a disadvantage of poor image quality. This decrease in color image density is believed to be due to the formation of harmful compounds from the development inhibitor precursors, which promote the degradation of the image-forming dyes. For this reason, it has been desired to develop a photographic element for color diffusion transfer that has a wide processing temperature tolerance range on both low and high temperature sides and does not reduce the image quality after processing. Therefore, the first object of the present invention is to:
The object of the present invention is to provide a photographic element for color diffusion transfer that provides color images of superior quality, and in particular, a color diffusion transfer method that provides color images with excellent stability (particularly low dark and thermal fading) during storage. Its purpose is to provide legal photographic elements.

A second object is to provide a photographic element for color diffusion transfer that has a wide processing temperature tolerance range. The present inventors have proposed a photosensitive sheet having an image receiving layer and a photosensitive layer comprising at least one silver halide emulsion layer in combination with a color image-providing substance on a support, and an alkali-treated composition. In a photographic element for color diffusion transfer, the element comprises a cover sheet comprising a neutralizing layer optionally in combination with a neutralizing timing layer on a separate support and a mechanism for ejecting the neutralizing layer into contact with the neutralizing layer.
On the side of the cover sheet substantially farthest from the support,
A barrier layer formed from a polymer latex obtained by using an ethylene monomer having at least one free carboxylic acid group, sulfonic acid group, or phosphoric acid group, or a salt thereof as one of the polymerization components is provided. It has also been found that the above objects can be effectively achieved by incorporating 1-phenyl-5-mercaptotetrazole into any layer between the barrier layer and the support of the cover sheet. .

Not only this, such photographic elements also have the advantage of lower manufacturing costs compared to traditional photographic elements using 5(2-cyanoethylthio)-1-phenyltetrazole. Here, the "barrier layer" refers to 1-phenyl-5
- means a layer that acts as a barrier to temporarily prevent mercaptotetrazole from coming into contact with photosensitive silver halide.

U.S. Patent 32 by Weyerts et al.
The use of 1-phenyl-5-mercaptotetrazole as a development inhibitor in photographic systems is known, as described in US Pat.

These prior art techniques are characterized by containing a development inhibitor in the image-receiving layer. However, although this can delay the development action, it is incomplete, so the purpose of reducing the minimum amount of developed silver is to reduce the maximum amount of developed silver, and it also has a development inhibiting effect at high temperatures. The above-mentioned U.S. Pat.
As described in No. 09029. Also, “Research Disc.
Volume 151, Volume 15162 (1976)
On page 86 of the issue (November 2013), it is stated that a layer made of latex may be used as a timing layer in a cover sheet, and that a layer made of latex may be used as a timing layer in a cover sheet, an image-receiving layer, or other layers other than the photosensitive layer. It is stated that a development inhibitor may be added.

However, not only the description of the addition position of the development inhibitor is general as described above, but also the description of the compound example is also general, with only a large number of heterocyclic thiols being listed. Furthermore, the use of development inhibitor precursors, especially 5-(2-cyanoethylthio)-1-phenyltetrazole, is strongly recommended here. Also, the 0LS
In the example of No. 2716505, the above precursor is also used as a means to widen the processing temperature tolerance range on the low and high temperature sides, and for this purpose, 1-phenol-5-menolecapto It is believed that adding tetrazole was previously believed to be an undesirable method. However, in the present invention, by specifically combining the specific barrier layer with 1-phenyl-5-mercaptotetrazole, not only can the processing temperature range of the photographic element be expanded, but also the development inhibitor precursor can be It is completely surprising that this excellent effect, which could not be expected from the known effect as a development inhibitor, can be obtained by preventing a decrease in dye image density during storage after processing, using a smaller amount than when using the dye and at a lower cost. It was the right thing to do. A preferred embodiment of the photographic element of the present invention is a so-called ``laminated integral type'' photographic film unit, in which an image-receiving layer, a white reflective layer, a light-shielding layer, and a color image-providing material are provided on a transparent support. At least one silver halide emulsion layer and a surface protection layer are coated in this order in combination with a neutralization layer, a neutralization timing layer, and the above-mentioned barrier layer on another transparent support. A photosensitive sheet consisting of a layered cover sheet having layers coated in this order, the photosensitive sheet having a bursting layer filled with an alkaline processing composition (including a developing agent and a light shielding agent). Possible items include those that have a built-in container (bag).

The container is located outside and in contact with the barrier layer and the surface protection layer, and is positioned such that the intended rupture opening of the container can spread the alkali treatment composition between these layers. It is preferable that the The 1-phenyl-5-mercaptotetrazole can be included in one or more of the neutralization layer, neutralization timing layer, or auxiliary layer in the cover sheet.

The auxiliary layer may be a layer provided for containing the tetrazole compound, or may be a layer provided for other purposes such as an adhesion improving layer.
The amount of the tetrazole compound added varies depending on the position of the layer to which it is added, the type of silver halide emulsion used, the type and film thickness of the barrier layer, but is approximately 0.01 mm01/d to approximately 10 mm01/M2. Appropriate, preferably 0
．． 1mm01/i to 2mm01/7rI.

As the barrier layer used in the present invention, a polymer latex (film-forming property Barrier layers formed using aqueous dispersions) are preferred.

Group A: Ethylene monomers having at least one free carboxylic acid group, sulfonic acid group, or phosphoric acid group, or a salt thereof.

Group B: - General formula (1): A monomer represented by

[In the formula,

Specifically, it is selected from the following monomers. Acrylamides, methacrylamides, vinyl ethers, vinyl ketones, allyl compounds, olefins, vinyl heterocyclic compounds, unsaturated nitriles, and polyfunctional monomers. Next A
The monomers of Group B and Group C will be explained in detail.

Group A monomers may have groups such as alkoxycarbonyl groups, aryl groups, and carbamoyl groups in addition to the above-mentioned acid groups.

Further, the acid group may be directly bonded to the carbon radical in the ethylene residue (MOiety), or may be bonded via an atom or an atomic group. Specific examples of the monomers of Group A include the following monofunctional monomers, but are not limited thereto.

Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
Monoalkyl itaconate (e.g. monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.)
, monoalkyl maleate (e.g. monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, etc.), citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (e.g. acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, acryloyloxybutylsulfonic acid, etc.), methacryloyloxyalkylsulfonic acid (such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid) acids, methacryloyloxybutylsulfonic acid, etc.), acrylamide alkylsulfonic acids (e.g. 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylethanesulfonic acid, etc.)
-acrylamido-2-methylpropanesulfonic acid, 2
-acrylamide-2methylbutanesulfonic acid, etc.),
methacrylamide alkyl sulfonic acid (e.g. 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.),
Acryloyloxyalkyl phosphates (e.g. acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.), methacryloyloxyalkyl phosphates (e.g. methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.) Such.

Further, the alkyl group in the acid monomer has, for example, about 1 to 8 carbon atoms.

These acids contain alkali metal ions (preferably Na+,
K+) or ammonium ion salts. B
In the general formula of the group, among the groups represented by R1 to R3, aliphatic groups are direct or branched alkyl groups (including cyclic ones)
and substituted alkyl groups.

The number of carbon atoms in the alkyl group is preferably 1 to 12. Substituted alkyl groups include aryl groups, aryloxy groups, halogen atoms, cyano groups, acyl groups, alkylcarbonyloxy groups, arylcarbonyloxy groups, and amino groups (including substituted amino groups; examples of substituents include alkyl groups, aryl group, etc. The number of substituents is 1 to 2), epoxy group, hydroxy group, alkoxy group, heterocyclic residue (heteroatoms include, for example, oxygen atom, nitrogen atom, sulfur atom, etc. As for the number of ring members) is preferably 5 to 6, and the ring may be unsaturated or saturated.An aromatic ring may be further fused to the heterocycle.
Furthermore, among the groups represented by R1 to R3, the aryl group naturally includes substituted phenyl groups and naphthyl groups,
Examples of the substituent include alkyl groups in addition to the substituents listed above for substituted alkyl groups.

Examples of monomers in Group B include monofunctional monomers such as vinylidene chloride, acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic acid esters, fumaric acid diesters, itaconic acid esters, and styrenes.

Furthermore, specific monomers include vinylidene chloride, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
Butyl acrylate, isobutyl acrylate, Sec
-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate,
2-phenoxyethyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate,
2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl Acrylate, 2.2-
Dimethyl-3-hydroxypropyl acrylate, 2-
Methoxyethyl acrylate, 3methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-1s0
-Propoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n-9), 1- Bromo 2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Sec-butyl methacrylate, amyl methacrylate, hexyl Methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-
Hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-1s0-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2
-methoxyethoxy)ethyl methacrylate, 2-(2
-ethoxyethoxy)ethyl methacrylate, 2-(2
-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added n = 6) glycidyl acrylate, glycidyl methacrylate, vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyl isobutyrate, vinyl dimethyl propionate, vinyl ethyl butyrate, vinyl valerate, vinyl caproate (VirFlcaprOate) Bi0)L
/'Chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate,
vinyl phenyl acetate, vinyl acetoacetate,
Vinyl lactate, vinyl mono-β-phenyl butyrate,
Vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene , cyclohexylstyrene, decylstyrene, benzylstyrene,
Chloromethylstyrene, trifluoromethylstyrene,
Ethoxymethylstyrene, acetoxymethylstyrene,
Methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorstyrene, dichlorostyrene, trichlorstyrene, tetrachlorstyrene, pentachlorstyrene, bromstyrene, dibromstyrene, iodostyrene, fluorostyrene, trifluorstyrene , 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene,
Vinylbenzoic acid methyl ester, butyl crotonate, hexyl crotonate, glycerin monocrotonate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dihexyl fumarate and monofunctional monomers such as dibutyl fumarate, but are not limited thereto.

Specific examples of monomers of group C are listed below, but are not limited to the following.

Acrylamides: For example, methylacrylamide,
Ethylacrylamide, propylacrylamide, isopropylacrylamide, butylacrylamide, Te
rt-butylacrylamide, heptylacrylamide, tert-octylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethyl acrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, hydroxyethylacrylamide, phenyl acrylamide, hydroxyphenylacrylamide, tolylacrylamide,
Naphthylacrylamide, dimethylacrylamide, diethylacrylamide, dibutylacrylamide, diisobutylacrylamide, N-(1,1-dimethyl-3
-oxobutyl)acrylamide, methylbenzylacrylamide, benzyloxyethylacrylamide, β
-cyanoethyl acrylamide, acryloylmorpholine, N-methyl-N-acryloylbiperazine, N-acryloylpiperidine, N-(1,1-dimethyl-3-
Hydroxybutyl) acrylamide, N-β-morpholinoethyl acrylamide, N-acryloylhexamethyleneimine, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, acrylhydrazine, etc.: Methacrylamides: For example, methylmethacrylamide, Ter
t-butylmethacrylamide, tert-octylmethacrylamide, benzylmethacrylamide, cyclohexylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide,
Dipropyl methacrylamide, hydroxyethyl-N-
Methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide, methacrylhydrazine, etc. Allyl compounds: For example, allyl acetate, allyl caproate, allyl pyrofurate, allyl laurate , allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, allyloxyethanol, allyl butyl ether, allyl phenyl ether, etc. Vinyl ethers: For example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether , ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-
Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, etc. Vinyl ketones: For example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc. Olefins: For example, synchropentadiene, ethylene, propylene,
1-Butene 1-benzene, 1-hexene, 4-methyl-1-benzene, 1-heptene, 1-octene, 1-decene, 5-methyl-1-nonene, 5,5-dimethyl-1-octene, 4 -Methyl-1-hexene, 4,4-dimethyl-1-benzene, 5-methyl-1-hexene, 4
-Methyl-1-hepetene, 5-methyl-1-hebutene,
Unsubstituted hydrocarbons such as 4,4-dimethyl-1-hexene, 5,5,6-trimethyl-1-heptene, 1-dodecene and 1-octadecene: vinyl heterocyclic compounds (heteroatoms include nitrogen atoms, The number of members of an oxygen atom, a sulfur atom, etc., and a heterocyclic ring is, for example, 5 to 6, and an aromatic ring may be further fused to this ring.

): For example, N-vinyloxazolidone, vinylpyridine, vinylpicoline, N-vinylimidazole, N-
Vinyl-2-methylimidazole, N-vinyltriazole, N-vinyl-3,5-dimethyltriazole, N-
Vinylpyrrolidone, N-vinyl-3,5-dimethylpyrazole, N-vinylcarbazole, vinylthiophene,
N-vinylsuccinimide, N-vinylglutarimide, N-vinyladipimide, N-vinylpyrrolidone, N-
Vinylpiperidone, N-vinyl-ε-caprolactam,
N-vinyl-2-pyridone, etc.; unsaturated nitriles;
For example, acrylonitrile, methacrylonitoile, etc.; polyfunctional monomer: for example, a plurality of vinyl groups (for example, 2 to
3), such as aliphatic or aromatic hydrocarbons with multiple vinyl groups (e.g. butadiene,
divinylbenzene), bis- or tri-α/β-unsaturated carbonyl compounds (e.g. diallyl phthalate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, and the chemical structures below) Compounds having: 1.j monomers (for example, acetoacetoxyethyl methacrylate described in JP-A-45-5819).

Among these monomers, from the viewpoint of monomer hydrophilicity, hydrophobicity, polymerization reactivity, stability of polymer latex, film-forming properties, etc., the monomers of Group A are acrylic acid, methacrylic acid, itaconic acid, and 2 -Acrylamido-2-methylpropanesulfonic acid, or phosphoric acid esters having vinyl polymerizable unsaturated functional groups such as those listed above (but having free phosphoric acid groups or salts thereof) are preferred. Among the monomers of Group B, vinylidene chloride, acrylic esters, methacrylic esters, and styrenes are preferred. The copolymer composition ratio of the polymer latex can be changed as appropriate depending on the properties desired for the color diffusion transfer photographic element to which the barrier layer formed using this latex is applied.

As for the Group A monomer component, as the proportion of the same component increases, the permeability of the barrier layer formed using this latex increases. The preferred amount of Group A monomer component is 0.1 x 10 - per gram of latex polymer solids.
It is between 3 mol and 2.2 x 10-3 mol. Particularly preferably, this component is in the range of 0.4.times.10@-3 mol to 1.0.times.10@-3 mol per gram of latex polymer solids. The group B monomer component is preferably 50 to 99% by weight, particularly 80 to 99% by weight of the latex polymer solid content.
is suitable. The C group monomer component is preferably 0 to 49% by weight, particularly preferably 0 to 19% by weight. The above monomer ratios are based on the relative proportions of the various monomers added into the polymerization reactor in conventional free radical polymerization processes. The barrier layer according to the present invention formed using the above latex preferably has an activation energy for permeation of an aqueous alkali solution of 18 KCa1/MOl or more, and a preferable polymer latex constituting this barrier layer is vinylidene chloride acrylonitrile- Acrylic acid copolymer latex-methyl methacrylate vinylidene monochloride-itaconic acid copolymer latex,
Vinylidene chloride-methyl methacrylate-acrylic acid copolymer latex, n-butyl methacrylate-acrylic acid copolymer latex, styrene-n-butyl acrylate-acrylic acid copolymer latex, methyl methacrylate-n-butyl methacrylate-itaconic acid Copolymer latex, styrene-ethoxyethyl acrylate-acrylic acid copolymer latex, styrene-n-butyl acrylate-acrylic acid monoglycidyl methacrylate copolymer latex, styrene-maleic acid di-1-n-
Butyl maleic acid copolymer latex, n-propyl acrylate-2-sodium methacryloyloxyethylsulfonate copolymer latex, vinylidene chloride-2
-methacryloyloxyethyl phosphate-methyl acrylate copolymer latex, Sec-butyl methacrylate-2-methacryloyloxyethyl phosphate copolymer latex, styrene-n-butyl acrylate acrylic acid-N-hydroxymethylacrylamide copolymer latex and other U.S. Patent No. 40563.
No. 94, No. 4061496, Patent Application No. 14858/1984
9, No. 52-144749, No. 53-35754, No. 53-46247, No. 53-46246, and the like.

The method for measuring the activation energy of permeation of an aqueous alkaline solution is as described in the aforementioned US Pat. No. 4,056,394.

The silver halide emulsion used in the present invention includes silver chloride,
A hydrophilic colloidal dispersion of silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof, in which the halogen composition is selected depending on the purpose of use and processing conditions of the photosensitive material. However, the iodide content is preferably 10 mol% or less.

The grain size of the silver halide used may be a normal grain size or a fine grain size, but it is preferable that the average grain size is in the range of about 0.1 micron to about 2 micron. Furthermore, depending on the intended use of the photosensitive material, it is desirable that the particle diameter be uniform. The crystal shape of the particles used may be cubic, octahedral or mixed crystal. These silver halide emulsions are, for example, P. Glafk
ides) by “Chimi Photoque (Chimi)”
ePhOtOgraItllqUe)” (2nd edition, 19
57; Paul MOntel. Paris) can be made by conventional methods such as those described in Chapters 18-23. The silver halide emulsion used in the present invention is a natural sensitizer contained in gelatin, a sulfur sensitizer such as sodium thiosulfate or N-N-N triethylthiourea, a gold thiocyanate complex salt, Chemical sensitization is preferably carried out by heat treatment in combination with a gold sensitizer such as a thiosulfate complex or a reduction sensitizer such as stannous chloride or hexamethylenetetramine.

In the present invention, even ordinary negative emulsions that tend to form latent images on the grain surfaces are developed in unexposed areas.

It is also used in so-called direct reversal silver halide emulsions (such as internal latent image type emulsions or solarization type emulsions). For solarization emulsions, see Mee
s edition “TheOryOfthePhOtOgra
phicPrOcesl (1942: McMlla
nCO. NewYOrk) on pages 261 to 297 are useful. Regarding the preparation method, for example, British Patent No. 443245, British Patent No. 462730,
U.S. Patent No. 2005837, U.S. Patent No. 2541472, U.S. Patent No. 3
No. 367778, No. 3501305, No. 350130
No. 6 and No. 3501307, etc. Regarding the internal latent image type direct positive emulsion, US Patent No. 249
7875, 2588982, 2456953, 3761276, 3206313, 3317322, 3761266, 3850637, 3923513
, 3736140, 3761267, 38549
It is described in No. 49, etc.

Direct reversal photographic emulsions are processed after image exposure in the presence of a fogging agent or as described in US Pat. No. 2,456,953 (KnOt
After the image exposure, a uniform exposure (high-light short exposure, i.e., shorter than 10-2 seconds, or low-light long exposure) is carried out during the surface development process as described in J.D. and Stevens). A positive image can be obtained directly by placing it on the lens and allowing it to overlap. It is preferable to use a fogging agent because the degree of fogging can be easily adjusted. The fogging agent may be contained in the sensitive material or may be added to the developer, but it is preferable to contain it in the sensitive material. As a fogging agent for this type of emulsion, US Pat.
No. 2568785, hydrazides and hydrazones described in No. 3227552, British Patent No. 1283835, Japanese Patent Publication No. 1983-38164
Typical examples include quaternary salt compounds described in US Pat. No. 3,734,738, US Pat. No. 3,719, and US Pat.

The amount of fogging agent used herein can vary widely depending on the desired result.

Generally, the concentration of this fogging agent when added to a photosensitive material varies depending on the fogging agent used, but is generally 0.
1η~1500~/1 mol Ag, preferably 0.5W9
It is used in the range of ~700η/1 mol Ag. When a fogging agent is added to the developing solution, it is generally about 0.05 to 5y (preferably 0.1 to 17y) per developer 11.
It is.

When a capping agent is included in any layer of a light-sensitive material, it is also effective to make the fogging agent diffusion resistant. An effective means for imparting diffusion resistance is to bond a ballast group commonly used in photographic couplers to a fogging agent. The silver halide emulsions used in the present invention can be stabilized with conventional stabilizers.

Furthermore, the silver halide emulsion used may contain a sensitizing compound such as a polyethylene oxide compound. The silver halide emulsion used in the present invention may be subjected to spectral sensitization as desired.

Useful spectral sensitizers include cyanines, merocyanines, holoporacyanines, styryls, hemicyanines, oxanols, hemiosaquinols, and the like. A specific example of the spectral sensitizer is the above-mentioned P. Glafkides, chapters 35-41 and F. M. Hamer
Author [TheCyanineandRelatedCOM
pOunds)] (Nterscience).

In particular, cyanines in which the nitrogen atom of the basic heterocyclic nucleus is substituted with an aliphatic group (e.g., an alkyl group) having a hydroxyl group, a carboxyl group, or a sulfo group, such as U.S. Pat. No. 3,177,210 are particularly useful in the practice of the present invention. Color image-providing materials for diffusion transfer methods used in combination with the photographic emulsion of the present invention include, for example, U.S. Pat. No. 3563739, No. 3658524, No. 3698897, No. 3725062, No. 3728113, No. 3751406, No. 3854945, No. 3880658, No. 3929760, No. 3931144, No. 3932381, British Patent No. 840
No. 731, No. 904364, No. 1038331, West German Patent Publication (0LS) No. 1930215, No. 2214381, No. 2228361, No. 2242762, No. 231713
No. 4, No. 2402900, No. 2406626, No. 2406653, No. 2406664, JP-A-49-1
No. 14424, No. 49-126332, No. 48-3382
No. 6, No. 49-126331, No. 50-115528,
No. 51-113624, No. 51-104343, 51-
No. 114930, No. 52-8827, No. 52-63324
No. 52106727, No. 53-23628, Japanese Patent Application No. 52-58318, No. 52-64533, No. 52-
No. 74601, No. 52-131278 "Research Disclosure"
re” magazine, volume 166, 16629 (published February 1978)
Various compounds can be used, including the dye developing agents described in, among others, which are initially non-diffusible, but after a redox reaction with the oxidation product of the developing agent, they cleave to form diffusible dyes. It is preferable to use a color image-providing substance of the releasing type (diffusible dye-releasing redox compound, hereinafter referred to as "DRR compound").

Specific examples of DRR compounds include those described in the above patent specifications, as well as magenta dye image-forming substances such as 1-hydroxy-2-tetramethylenesulfamoyl-4-[3'-methyl-4'( As a dye image-forming substance, 1-phenyl-3-cyano-4-3/
1[ghydroxyl-methyl-5X-(-2″2・4
Examples include 1'5-di-t-pentylphenoxyacetamino)-phenylsulfamoylphenylazo}-5 pyrazolone.

When using a DRR compound in the present invention, any silver halide developer can be used as long as it can cross-oxidize the DRR compound.

Such a developer may be included in the alkaline processing composition (processing element) or in an appropriate layer of the photosensitive element. Examples of developing agents that can be used in the present invention are as follows. Hydroquinone, aminophenols, such as N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-oxymethyl-3-pyrazolidone, N·N-diethyl-p-phenylenediamine, 3-methyl-N-N-diethyl-p-phenylenediamine, 3-methoxy-N-
Ethoxy-p-phenylenediamine and the like. Among those listed here, black and white developers are particularly preferred, as they generally have properties that reduce stain formation in the image receiving layer (mordant layer).

Furthermore, the DIR reversal emulsion system as described in U.S. Pat.
A transfer positive image can also be obtained by a reversal emulsion system using dissolution physical development as described in No. 364.

U.S. Patent Nos. 3,227,550 and 3,227,552;
A series of processes for obtaining color diffusion transfer images are described, such as in British Patent No. 1330524.

When using the diffusible dye releasing agent in the present invention, as a color developing agent, US Pat.
Paraphenylenediamine derivatives described in No. 59643 and No. 3813244 are representative.

Furthermore, p-aminophenol derivatives such as those described in JP-A-48-26134 can also be usefully used. Photographic elements of this invention have supports that do not undergo significant dimensional changes during processing.

Examples of such supports include cellulose acetate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, etc. which are used in common photographic materials. Besides that,
Useful supports include, for example, paper and paper laminated on the 1y surface with a water-impermeable polymer such as polyethylene.

The processing composition used in the present invention is a liquid composition containing processing components necessary for developing a silver halide emulsion and forming a diffusion transfer dye image, and the solvent is mainly water and other It may also contain a hydrophilic solvent such as methanol or methyl cellosolve.

The processing composition maintains the pH necessary for development of the emulsion layer and removes acids generated during the development and dye image formation processes (e.g., hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid). Contains a sufficient amount of alkali to neutralize acids (acids, etc.). As the alkali, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, phosphoric acid 3
Alkali metal or alkaline earth metal salts such as sodium, diethylamine, or amines are used, preferably having a pH of about 12 or higher at room temperature, especially PHL.
It is desirable to contain caustic alkali at a concentration of 4 or more. More preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers can be added to the treatment composition at room temperature in an amount of 1 or more, preferably several hundred (500 to 600)
It gives a viscosity of about 0.00 to 1000 poise, and not only facilitates the uniform spread of the composition during processing, but also allows the aqueous solvent to migrate to the photosensitive element and image receiving element during the processing process, thereby concentrating the processing composition. Sometimes a non-flowing film is formed to help the film units unite together after processing. This polymer film can also be used to inhibit further migration of colored components to the image-receiving layer after the formation of the diffusion-transferred dye image is substantially completed, thereby preventing changes in the image.
In addition, the processing composition may contain light-shielding agents such as TiO2, carbon black, and PH indicator dye to prevent fogging of the silver halide emulsion by external light during processing, as well as U.S. Pat. No. 3,579,333. It is advantageous to contain desensitizers such as those described in .

The above treatment composition is disclosed in U.S. Pat.
No. 643886, No. 2653732, No. 272305
No. 1, No. 3056491, No. 3056492, No. 3
It is preferable to use it in a rupturable container as described in No. 152515 and the like. ΣThe mordant used in the image-receiving layer for fixing the diffusible dye produced from the dye image-providing substance includes U.S. Pat.
No. 70439, No. 3709690, No. 3547649
No. 3,898,088, No. 3,958,995, JP-A-50-71332, etc. are used.

It is preferable to use a film-forming acidic polymer in the neutralizing layer, and any such acidic polymer can be used.

Examples of acidic polymers include monobutyl ester of a copolymer of maleic anhydride and ethylene, monobutyl ester of a copolymer of maleic anhydride and methyl vinyl ether, monoethyl ester of a copolymer of maleic anhydride and ethylene, and Monopropyl ester of a copolymer, monopentyl ester of the same copolymer, monohexyl ester of the same copolymer, monoethyl ester of a copolymer of maleic anhydride and methyl vinyl ether, monopropyl ester of the same copolymer, Monobenzyl esters of the same copolymers, monohexyl esters of the same copolymers, polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid in various ratios, acrylic acid or methacrylic acid and other vinyl-based Copolymers with monomers, such as acrylic esters, methacrylic esters, vinyl ethers, acrylamides, methacrylamides, etc., preferably having an acrylic acid or methacrylic acid content of 50 to 90 mol% are used. be able to. Regarding the neutralizing layer, U.S. Pat. No. 3,362,819, U.S. Pat.
There are also descriptions in Patent No. 3,819,371 and French Patent No. 2,290,699. Among these, it is recommended to use polyacrylic acid and acrylic acid monobutyl acrylate copolymer. For example, gelatin, polyvinyl alcohol, polyacrylamide, partially hydrolyzed polyvinyl acetate, a copolymer of β-hydroxyethyl methacrylate and ethyl acrylate, or acetyl cellulose are used as main components in the neutralization timing layer. , and other US patents 3
No. 455686, No. 3421893, No. 378581
5, No. 3847615, No. 4009030, and JP-A-52-14415 can also be used.

Reference Example (5) Red-sensitive internal latent image type direct positive silver iodobromide emulsion (internal latent image type emulsion prepared by the method described in U.S. Pat. No. 3,761,276: silver halide... halogen composition: iodine 2 mol%, A photosensitive sheet coated on a polyethylene terephthalate transparent support as follows [
A] was produced.

(1) A mordant layer containing a polymer containing the following repeating units in the following proportions and gelatin (3,07/771). (2)
A white reflective layer containing titanium oxide 207/m and gelatin 2.07/m. (3) Carbon black 2.707/
A light blocking layer containing M2 and gelatin 2.707/Trl.

(4) The following cyan DRR compound (0.447/TI)
, 2,5-di-t-butylhydroquinone (0.015
7/Rrl), diethyl laurylamide (0.117/
m') and gelatin (1.17/i).

Fogging agent (6) A layer containing gelatin (1.97/l) and 2,5-di-t-pentadecylhydroquinone (0.857/l).

(7) The following magenta DRR compound (0.6t/i),
2,5-di-t-butylhydroquinone (0,01V/
TI), diethyl laurylamide (0.13y/TI)
and a layer containing gelatin (1.17/I).

:． (8) Green-sensitive internal latent image type direct positive silver iodobromide emulsion (
Internal latent image type emulsion prepared by the method described in U.S. Pat.
/TI), fogging agent used in layer (5) (0.05~
/Trl) and 5-bentadecylhydroquinone-2
- sodium sulfonate (0.157/TI).

(9) A layer containing gelatin (1.9 f/d) and 2,5-di-t-pentadecylhydroquinone (1.37 f/d).

(Substitute) The following yellow-DRR compound (0.91y/y)
, diethyl laurylamide (0.15t/d), 2.5
-Di-t-butylhydroquinone (0.0127/I)
and a layer containing gelatin (0.9f7/m'').

Internal latent image type emulsion: ・Rogen composition in silver halide: iodine 2 mol%, silver amount 2.67/M2, gelatin 2
．． 77/ Fogging agent used in the scarring layer (5) (0.11η
/wl') and 5-pentadecyl-hydroquinone-
A layer containing sodium 2-sulfonate (0.16 V/m゛).

(Serial) A layer containing gelatin (1.07/m”).

Cover sheet A cover sheet (A) was prepared by coating polyethylene terephthalate on a transparent support in the following order.

(1) A neutralization layer coated with acrylic acid-butyl acrylate (mole ratio 8:2) copolymer having an average molecular weight of 50,000 at a rate of 227 per square meter. (2) Degree of acetylation 39.4
Neutralized timing layer coated with % acetylcellulose 3.87/m and poly(styrene-co-mono-maleic anhydride) (composition ratio, styrene:mono-maleic anhydride) (composition ratio, styrene:mono-maleic anhydride) (molecular weight: about 10,000) 0.27/m'' .

In the cover sheet (A) as the cover sheet (B), 1-phenyl-5-mercaptotetrazole (hereinafter referred to as "PMT") 0.45 mm01 is contained in the neutralized timing layer.
/M2 (80.17f9/Rrl) was prepared.

In the cover sheet (4) as the cover sheet (C), 0.45 mm of 5-(2-cyanoethylthio)-1-phenyltetrazole (hereinafter referred to as "CPT") described in U.S. Pat. T
A cover sheet to which i' (104 i/m") was added was prepared.

★The processing solution with the above composition was added to 0.
87 pieces were filled into pressure-rupturable containers. Processing process Each of the above cover sheets and the above photosensitive sheet [A] were overlapped and a color test chart was exposed from the side of the cover sheet, and then the above processing solution was spread between both sheets to a thickness of 85 μm. (Unfolding was done with the help of pressure rollers).

Treatments were carried out at 25°C and 35°C. After processing, the blue density (B) generated in the image-receiving layer is observed through the transparent support of the photosensitive sheet.
, green density (G), and red density (R) were measured using a Maghes reflection densitometer one hour after treatment, and the transferred color image densities as shown in Table 1 were obtained. As shown in Table 1, in this experimental system that does not use a barrier layer, although the minimum concentration (Drnin) decreases with cover sheet B containing PMT, it also decreases to the maximum concentration (1) Nax). Therefore, use CTP that lowers the minimum density without lowering the maximum density too much. 5
It can be seen that it is inferior to the cover sheet C that was prepared.

A cover sheet was prepared according to Example 1 below.

Coatings were carried out on the coversheet polyethylene terephthalate support in the following order: 10.

(1) The same neutralization layer as that of cover sheet A in the reference example.

★)． ) The degree of acetylation of acetylcellulose is 37.3
The neutralization timing layer is the same as that of the reference example cover sheet A, except that it is %. Barrier layer coated with the latex shown in Table 2 below.

Furthermore, PMT or CPT was added as an additive (the addition position and amount are shown in Table 2), and cover sheets (D to (YQ) as shown in Table 2) were prepared.

Claims (1)

[Claims] 1 A photosensitive sheet having on a support a photosensitive layer comprising at least one silver halide emulsion layer in combination with a color image-providing material and an image receiving layer, a mechanism for releasing an alkaline processing composition, and another A color diffusion transfer photographic element comprising a cover sheet having a neutralizing layer on a support, optionally in combination with a neutralizing timing layer, the cover sheet having, on its side substantially furthest from the support, "
A barrier layer formed from a polymer latex obtained by using an ethylene monomer having at least one free carboxylic acid group, sulfonic acid group, or phosphoric acid group, or a salt thereof as one of the polymerization components, and 1- in any layer between the barrier layer and the support of the cover sheet.
A photographic element characterized in that it contains phenyl-5-mercaptotetrazole.