JPS5917411B2 - Photographic elements for color diffusion transfer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a color diffusion transfer method with a neutralization system.
The present invention relates to photographic elements for DTR color (hereinafter referred to as DTR color), and more particularly to DTR color photographic elements having a novel timing layer.

Conventionally, in DTR colors, it is well known that after a diffusible dye or dye developer is transferred to a mordant layer as a result of development with an aqueous alkaline developer, a neutralizing layer is provided to lower the surrounding pH. There is.

However, if the pH drops early due to the provision of a neutralizing layer, development will be hindered.
It is also well known that a layer that temporally controls the H reduction, that is, a "timing layer" is used in combination with a neutralization layer.

There are two main types of neutralization systems that include these layers:
One uses a timing layer whose water permeability is inversely proportional to temperature, and the other uses a timing layer whose water permeability is directly proportional.

In the present specification, "water permeability" means the property of substantially allowing an aqueous alkaline developer to pass through, and more specifically, the PH indicator (thymol phthalein) coated film of Example 2 described later, When the PH indicator-coated film becomes colorless after facing the timing layer on the neutralization layer and spreading an alkaline viscous liquid therebetween, it means that the timing layer is water permeable.

When using a timing layer whose water permeability is inversely proportional to temperature, the duration of high PH (preferably above PHIO) to develop the silver halide and form an imagewise distribution of diffusible dye increases with increasing temperature.

The basic idea of a neutralization system using a timing layer that exhibits such temperature dependence was proposed in Japanese Patent Publication No. 15756/1973, and the specific material for the timing layer was proposed in U.S. Patent No. 3,421,893. Ya No. 357570
Examples include the polyvinylamide polymer described in No. 1.

Neutralization systems using these materials as a timing layer so that the duration of high PH increases with increasing temperature are described in U.S. Pat.
In the color diffusion transfer method using a dye developer described in No. 44 and No. 3,415,645, an excessive amount of dye is adsorbed to the mordant layer at low temperatures when the development and the diffusion rate of the dye developer are fast. It is useful when applied to the color diffusion transfer method, which has some disadvantages. On the other hand, a type of neutralization system using a timing layer whose water permeability is directly proportional to temperature and in which the high PH duration becomes shorter as the temperature rises is disclosed in Japanese Patent Laid-Open No. 48-3.
No. 3826, U.S. Patent No. 3929760, U.S. Patent No. 39311
44, No. 3,932,381, which are initially non-diffusible but release diffusible dyes by redox or coupling reactions with oxidation products of the developing agent. Substance (hereinafter referred to as "the former")
DRR compounds, the latter referred to as "DDR couplers," are useful in color diffusion transfer processes.

In other words, the reduction in the density of transferred color images due to delays in silver halide development at low temperatures, delays in the above-mentioned redox reactions, and delays in dye diffusion can be prevented by extending the high pH duration (i.e., silver halide development, dye release and transfer). possible extension of time)
It can be corrected by In this type of timing layer, water permeability increases with increasing temperature,
The timing layer made of polyvinyl alcohol described in U.S. Pat.
re)” magazine, page 86, and U.S. Patent No. 4056394, U.S. Patent No. 40
61496 (i.e., a timing layer formed from a latex of methyl acrylate monochloride vinylidene itaconic acid copolymer, or acrylonitrile vinylidene monochloride-acrylic acid copolymer) and other patent applications filed in 1983. -Styrene-n described in specification -148589
-Butyl acrylate-acrylic acid copolymer latex and styrene-butyl acrylate-acrylic acid monoglycidyl acrylate copolymer latex described in Japanese Patent Application No. 52-144749. .

However, in the timing layer described in JP-A-49-22935, the degree of decrease in water permeability on the low temperature side is low, and the development delay cannot be sufficiently compensated for.

Also, the above “ResearchDisclOsure”
magazine and U.S. Patent Nos. 4,056,394 and 4,061,496,
The timing layer made of latex described in the specifications of Japanese Patent Applications No. 51-148589 and No. 52-144749 satisfies the function of greatly reducing water permeability at low temperatures, and is sufficient to prevent delays in development at low temperatures. However, polymer latex membranes have a fatal drawback as a timing layer for the purpose of controlling water permeability.
In other words, if a film made of polymer latex is made by completely fusing the particles, it will have extremely low water permeability and cannot be used as a timing layer for color diffusion transfer photographic materials. Therefore, when the timing layer of a color diffusion transfer photographic material is made from a polymer latex, it is necessary to create an incomplete film with many holes when viewed microscopically without completely fusing the polymer particles. However, this film still continues to fuse due to heating and changes over time, so when storing it for many years or when partially heating it by heat sealing when forming a film unit, part or all of the screen may be damaged. Over time, the water permeability of the timing layer decreases, which may delay the stop of development and cause malfunctions such as fogging and staining due to overdevelopment. SUMMARY OF THE INVENTION It is an object of the present invention to provide a DTR color photographic element having a novel timing layer that reduces fog and staining upon heating and aging.

Another object is to provide a DTR color photographic element having a timing layer suitable for high speed mass production by heat sealing.

The above object is a neutralization system for lowering the pH of an aqueous alkaline developer [this neutralization system includes a neutralization layer and a timing layer, in which the developer passes through the timing layer to It is placed over or under (directly or indirectly) the neutralizing layer in such a positional relationship that it reaches the neutralizing layer.

] in the photographic element for color diffusion transfer method, the timing layer is formed from at least one type of polymer latex (film-forming aqueous dispersion) represented by the following general formula 1 (the polymer latex The layer is water permeable). General formula 1: [In the formula, R1 is hydrogen or a methyl group, z is 1C-0
R2-0P-0M, R2 is an alkylene group having 2 to 10 carbon atoms or +R3-0+R3, NR3 is an alkylene group having 2 to 6 carbon atoms, and A is a copolymerizable unsaturated monomer component.

Here, the alkylene group may be branched or may have a substituent [for example, a halogen atom (chlorine, fluorine, etc.), an alkoxy group (methoxy, ethoxy, etc.), an aryl group (phenyl, etc.)] . Also, A. b. c is the copolymerization monomer ratio (wt%), and a is 5.
0-901 b is 0.5-20, c is O-50.

n is an integer from 1 to 5.

M represents a hydrogen atom, an alkali metal or an ammonium radical (NH4).

] Examples of polymerizable monomers that provide the component represented by CH2-C+ in general formula 1 include 2-acryloyloxyethyl phosphate, 1-methyl-2
-acryloyloxyethyl phosphate, 2-acryloyloxyethoxyethyl phosphate, 4-acryloyloxybutyl phosphate, 2-methacryloyloxyethyl phosphate, 1-methyl-2-methacryloyloxyethyl phosphate, 1-chloromethyl 2
-methacryloyloxyethyl phosphate, 2-methacryloyloxyethoxyethyl phosphate, 4-methacryloyloxybutyl phosphate, and the like.

Among these, 2-acryloyloxyethyl phosphate and 2-methacryloyloxyethyl phosphate are particularly preferred. Polymerizable monomers that provide the component represented by -(-A+ in general formula 1 include acrylic esters, methacrylic esters, acrylamide, methacrylamide, allyl compounds, vinyl ethers, vinyl esters, vinyl heterocyclic compounds, styrenes, Vinyl ketones, unsaturated nitrites, olefins, maleic esters, fumaric esters, itaconic esters, crotonic esters, etc.More specific examples include acrylic esters, such as methyl acrylate, ethyl acrylate, n- Propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, 2
-chloroethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, ethylene glycol diacrylate, Triethylene glycol triacrylate, trimethylolpropane triacrylate, 2-
Methoxyethyl acrylate, 2-ethoxyethyl acrylate, etc.: Methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, acetoacetoxyethyl methacrylate , chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, diethylene glycol dimethacrylate, triethylene glycol trimethacrylate,
Trimethylolpropane trimethacrylate, pentaerythritol monomethacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, etc.; acrylamides, such as acrylamide methyl acrylamide, ethylacrylamide, butylacrylamide, tert-butylacrylamide, methoxyethylacrylamide, dimethylacrylamide , diethyl acrylamide, dibutylacrylamide, acryloylmorpholine, N-acryloyl biverizine, acrylhydrazine, etc.: methacrylamides, e.g.
Methacrylamide Methyl methacrylamide, Tert-
Butyl methacrylamide, benzyl methacrylamide,
Phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, hydroxyethyl-N-
Methyl methacrylamide, N-methyl-N-phenyl methacrylamide, methacrylhydrazine, etc.; allyl compounds such as allyl ethers and allyl esters;
For example, allyl acetate, allyl caproate, allyl pyrofurylate, allyl benzoate, allyl acetoacetate, allyl lactate, diallyl inphthalate, etc., allyl butyl ether, allyl phenyl ether, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, vinyl esters, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate,
Vinyl dichloroacetate, vinyl methoxyacetate, vinyl acetoacetate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, etc.; vinyl heterocyclic compounds, such as N-vinyloxazolidone, vinylpyridine, vinylpicoline, N-vinylimidazole, N-
Vinylpyrrolidone, N-vinylcarbazole, etc.; Styrenes, such as styrene, methylstyrene, chloromethylstyrene, trifluoromethylstyrene, acetoxymethylstyrene, methoxystyrene, chlorstyrene, dichlorostyrene, divinylbenzene, vinylbenzoic acid methyl ester Crotonic acids such as crotonic acid amide, crotonic ester, etc., such as butyl crotonate, hexyl crotonate, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone,
methoxyethyl vinyl ketone, etc.; olefins, such as synchropentadiene, ethylene, vinyl chloride,
Chloroprene, butadiene, vinyl bromide, propylene,
1-Butene, 1-benzene, 1-hexene, 1-octene, 5,5-dimethyl-1-octene, etc.; Itaconic acid esters, such as diethyl itaconate, dibutyl itaconate, etc.; Maleic acid esters, such as maleic acid Acid monomethyl, diethyl maleate, dibutyl maleate, dioctyl maleate, etc.; fumaric acid esters, such as monomethyl fumarate, diethyl fumarate,
Dihexyl fumarate, dibutyl fumarate, dioctyl fumarate, etc.; unsaturated nitriles such as acrylonitrile, methacrylonitrile, etc., and one or more of them can be used as necessary.

Among these monomers, acrylic esters are preferred from the viewpoint of polymerizability, emulsifying properties, film-forming properties of polymer latex, etc. Preferred are methacrylic acid esters, vinyl esters, acrylonitrile, methacrylonitrile, vinyl chloride, and the like. The copolymer composition ratio of the polymer latex can be arbitrarily selected depending on the desired characteristics of the photographic system using it.

Regarding b, as the content of this component increases, the water permeability of the layer made of this latex increases in a photographic system using this component. The component ratio a is preferably 60 to 90% by weight, particularly preferably 70 to 88% by weight.

b is preferably 2 to 15% by weight, particularly preferably 3 to 10% by weight. Further, c is preferably 2 to 40% by weight, particularly preferably 5 to 20% by weight. The monomer component ratios described herein are based on the weight ratios of the various monomers used in conventional free radical polymerization.

Therefore, the proportion of monomer components in the polymer produced by this polymerization will differ to some extent from the proportion of monomers used, for reasons well known to those skilled in the art of making polymer latexes. Next, typical examples of the polymer latex used in the present invention will be listed.

(1) Vinylidene chloride-2-methacryloyloxyethyl phosphate to methyl acrylate copolymer (weight ratio 80:8:12) (2) Vinylidene chloride-2-acryloyloxyethyl phosphate to butyl acrylate copolymer (weight ratio 75:10:15) (3) Vinylidene chloride-2-methacryloyloxyethyl phosphate butyl methacrylate copolymer (weight ratio 85:5:10)
(4) Vinylidene chloride-2-methacryloyloxyethyl phosphate-acrylonitrile copolymer (weight ratio 8
3:JMeF10) (5) Vinylidene chloride-2-acryloyloxyethyl phosphate ethyl acrylate copolymer (weight ratio 82:6:12) IU (6) Vinylidene chloride-2-methacryloyloxyethyl phosphate copolymer Acetate copolymer (weight ratio 9
0:JMeF3) (7) Vinylidene chloride-2-methacryloyloxyethyl phosphate-12-hydroxyethyl acrylate copolymer (weight ratio 87:4:9) (8) Vinylidene chloride-4-acryloyloxybutyl phosphate Tho-methyl methacrylate copolymer (weight ratio 88: J method)
F5) (9) Vinylidene chloride-1-methyl-2-methacryloyloxyethyl phosphate copolymer (weight ratio 8
7:13) 4 Vinylidene chloride-2-methacryloyloxyethyl phosphate to diethyl maleate copolymer (weight ratio 85:8:7) (auto) Vinylidene chloride-2-methacryloyloxyethyl phosphate to styrene copolymer ( Weight ratio 88:8:4) (auto) vinylidene chloride-2
- Methacryloyloxyethyl phosphate-acrylonitrile-ethyl acrylate copolymer (weight ratio 75:
5: JMeF13) U vinylidene chloride-2-acryloyloxyethyl phosphate-butyl methacrylate-hydroxymethyl methacrylamide copolymer (weight ratio 78:
JMeF12:3) (auto) Vinylidene chloride-2-memethryloyloxyethyl phosphate-butyl acrylate methacrylonitrile copolymer (weight ratio 72:4:12:
12) (Auto) Vinylidene chloride-2-methacryloyloxyethyl phosphate vinyl monochloride-methyl acrylate copolymer (weight ratio 78:JMeF10:5) The polymer latex used in the present invention is used in the field of polymer synthesis. can be synthesized by methods well known to those skilled in the art.

For example, US Patent No. 2914499, US Patent No. 30338
No. 33, No. 3547899, Canadian Patent No. 704
No. 778 and Japanese Patent Application No. 51-148589 "Encyclopedia of Polymer Science and Technology (Encyclopedia of Polymer Science and Technology)"
ersciencemltechnOlOgy)"L4
548, "Plastic Materials Course" 13 Vinylidene Chloride Resin, "High Polymers"
The polymer latex used in the present invention can be easily synthesized by referring to s''γA (3) 1269. The particle size of the timing layer latex of the present invention is on average 0.
．． It is preferably about 0.05 to 0.4μ, particularly preferably about 0.05μ.
0.05 to 0.2 μm, but it can be appropriately adjusted as needed, and there is no particular restriction. (This average particle size is determined by measuring the diameter of the particles using a microscope and taking the number average of these.

). The timing layer of the present invention can be provided by directly or indirectly applying at least one of the polymer latexes produced by the method described above directly or indirectly onto the neutralizing layer, either in its original concentration or diluted appropriately with water. Here, "indirectly" means that the timing layer of the present invention is applied onto the neutralization layer via another timing layer (for example, a cellulose acetate layer) or an adhesion improving layer. Examples of the adhesion improving layer include a layer containing hydrophilic colloid such as gelatin and polyvinyl alcohol.

This layer can also serve as a timing layer.

Neutralizing layers used in conjunction with the timing layer of the present invention include acidic polymers such as the semi-n-
Butyl ester, polyacrylic acid, acrylic acid and n
-Butyl acrylate, etc., as well as U.S. Patent 258403
Good results are obtained by using the solid acids or metal salts (zinc acetate, zinc sulfate, magnesium acetate, etc.) shown in specification No. 0. The neutralizing layer formed by such a material stabilizes the dye image by lowering the pH of the film unit after development, stopping development, and greatly reducing the subsequent transfer of the dye image. be. Photographic elements of the present invention include a cover sheet for overlaying the "photosensitive element", provided that a neutralization system is incorporated.

), or a photosensitive sheet consisting of an "image receiving element" and a "photosensitive element" coated sequentially on a support, a "cover sheet" having a neutralization system, and a combination of the photosensitive element and the cover sheet. Even if it is a so-called laminated integrated film unit, in which the [processing elements] are integrated in order to be spread between the two (however, these elements may be detachable as necessary). However, such a film unit is preferable. Further, the photographic element of the present invention is of a type in which development processing is extended between an image receiving element coated on a support and a member coated on the support in the order of a neutralizing layer, a timing layer, and a photosensitive element. It may be of.

The timing layer latex of the present invention can be coated by a known method, such as a spiral rod coater, an extrusion coater, a dip coater, an air knife coater, or the like.

Various additives can be mixed into this latex depending on the purpose.

However, when producing the latex and forming the timing layer from the latex, it is preferable not to add any water-soluble additives other than the surfactant. The above additives include surfactants to improve wetting during coating, solvents to facilitate film formation (e.g. methyl cellosolve, ethyl cellosolve, cyclohexanone, toluene, etc.), and prevent adhesive failure during manufacture and use. Matting agents such as powdered silica and bead-like polymers are used to prevent this from occurring, fillers (e.g. colloidal silica, titanium dioxide, carbon black, diatomaceous earth, etc.) are used to improve the strength of the film, and they are used to improve the flexibility of the film. It is desirable to use a plasticizer (for example, phthalate esters such as dibutyl phthalate and dihexyl phthalate, phosphoric acid esters such as trialkyl phosphate and tricresyl phosphate) to improve the quality, depending on the purpose.

The amount of the above additive to be used is selected depending on the purpose, but preferably 0.1 to 20% (per solid content of latex polymer).
(weight), particularly preferably 1 to 10% (weight). However, the preferred amount of the surfactant used to improve wetting is about 0.05 to 0.5%. The polymer latex for forming the timing layer of the present invention may be mixed with other polymer latexes having good compatibility, if necessary.

For example, for the purpose of increasing the flexibility of the film or improving the surface smoothness, other polymer latexes having the necessary polymer properties can be mixed and used. In this case, the weight ratio of the other polymer latex to the polymer latex for forming the timing layer of the present invention is 0.1 to 200.
It is preferably used in a range of approximately 1% to 1%.
It is preferable to use it within a range of 100%, but there is no particular limitation. The thickness of the timing layer of the present invention is preferably from 0.5 to
The thickness is 20μ, particularly preferably 2 to 8μ, but can be freely selected as required and there is no particular restriction.

Preferred drying methods for applying the timing layer of the present invention include a method using electromagnetic waves such as infrared rays and ultrashort waves, a contact heat transfer method such as a method using a heat drum, and a method using hot air. Regardless of the method used, it is desirable to create a transparent film with an amount of energy that slightly exceeds the minimum energy required to create a transparent film from latex, and then dissipate the remaining moisture and other volatile components by applying a sufficiently large amount of energy. .

If an excessive amount of energy is applied during drying before a sufficient film has been formed, volatile components such as moisture may evaporate rapidly and cause boiling. In such cases, the resulting timing layer film has many defects such as holes. At defective locations, the permeation of the alkaline solution into other locations may become extremely rapid, which may result in spot-like defects in the photographic image. Since the latex for the timing layer of the present invention forms a transparent film at a relatively low temperature, a very uniform film with few defects can be obtained if it is dried by the method recommended by the inventors as described above. As mentioned above, drying conditions are important when forming the timing layer used in the present invention.

It is essential to carry out the present invention that the drying conditions for forming the polymer latex timing layer used in the present invention are within a range that allows the polymer latex layer to be water permeable. The temperature applied for this drying is approximately 50°C
The temperature is preferably about 120°C.

The timing layer used in the present invention can control the rate of alkali absorption by the neutralization layer, and also allows diffusion and movement of substances in the layer on the opposite side of the silver halide emulsion layer with respect to the timing layer used in the present invention. can also be controlled.

This "layer on the opposite side" is, for example, a neutralization layer.
So, to explain the neutralization layer, development inhibitors and their precursors (development inhibitor-releasing couplers, hydroquinone, and other compounds that release development inhibitors upon hydrolysis, such as those described in French Patent No. 2,282,124). It is preferable to mix a reducing agent for preventing photofading into the neutralizing layer in advance (however, if these agents diffuse into the silver halide layer at the initial stage of development, they will cause unfavorable chemical effects). By applying a timing layer, it is possible to prevent them from reaching the silver halide emulsion layer at the beginning of development, and to allow them to act after development has proceeded sufficiently. Of course, the effect of these additives can also be made temperature independent. For example, if a development inhibitor or its precursor is mixed into the neutralization layer in order to suppress excessive development, development will not be inhibited at the start of development at any temperature, but after development has sufficiently progressed. Development can be suppressed and eventually stopped. This can prevent the occurrence of stains and increase in image density due to excessive development. In particular, when the development temperature is high, the development speed is very fast and stains are likely to occur due to overdevelopment. The use of a timing layer is suitable for preventing the above-mentioned disadvantages. As a development inhibitor releasing coupler (DIR coupler),
For example, US Pat. No. 3,227,554, US Pat. No. 3,617,291
No. 3701783, No. 3790384, No. 36
No. 32345, West German patent application (0LS) 2414006
No. 2454301, No. 2454329, British Patent No. 953454, and Japanese Unexamined Patent Publication No. 52-69624 can be used.

Other compounds that release development inhibitors during development include, for example, US Pat. Nos. 3,297,445 and 337.
No. 9529 and West German patent application (0LS) No. 2417914 can be used.

Using the timing layer of the present invention, high P on the low temperature side
The H-lasting effect is particularly remarkable. Also, moderately high pH
By adjusting the duration of , the decrease in transferred image density can be almost completely corrected, so that a constant transferred image density can be obtained regardless of changes in processing temperature. Also,
When the timing layer of the present invention is used, the water permeability increases significantly with increasing temperature, extending the measurement temperature range from 0°C to 40°C.
When the temperature is set within this range, the effect is obtained that the water permeation rate can be increased by 2.5 times or more for every 10° C. rise in temperature.

This effect makes it easier for the processing liquid to pass through the timing layer used in the present invention and reach the neutralization layer at high temperatures.
The pH of the processing solution quickly decreases and excessive development is suppressed.
In other words, there is an advantage that it is possible to prevent excessive transferred images from being obtained. Furthermore, the timing layer used in the present invention has high film strength and will not be cut near the interface with the adjacent layer even when subjected to external mechanical action.
It has the feature that it does not peel off during the manufacturing process or during photography, and the film and film unit are not easily damaged by cutting.

In addition, the timing layer hot melt adhesive used in the present invention has a high adhesive strength after heat sealing, so it has the advantage of facilitating high-speed mass production of film units using a heat seal processing system. has. The photographic element having the timing layer of the present invention can be easily heat-sealed using any commonly known hot-melt adhesive.

In this case, the hot-melt adhesive layer coated on the support and the timing layer side of the photographic element containing the timing layer used in the present invention are combined and heat-sealed by sandwiching them between heated metal blocks. be exposed. In addition to hot melt adhesives such as polyethylene vinyl acetate adhesives, research
It is particularly advantageous to use an adhesive such as that described in vol. 158, Taki No. 15839, published June 1977, by applying the adhesive to soil such as polyethylene terephthalate film, polycarbonate film, or triacetyl cellulose film.

Peel strength after heat sealing can be easily measured using a normal tensile tester. Further, in producing the latex used in the present invention, it is advantageous that the production cost is low because it can be produced using inexpensive raw materials and simple equipment.

Furthermore, when using the latex of the present invention, while a large amount of water remains in the coating film during drying, it is gradually dried under relatively low temperature conditions to form a film with few defects, and then the latex particles are dried under high temperature conditions. Since the film of the timing layer is completed by sufficiently fusion bonding, there is also the advantage that defects that may cause malfunctions in photographic images can be eliminated. The usefulness of the timing layer of the present invention, whose water permeability increases significantly as the temperature rises, can be evaluated by comparing the temperature change in photographic development with the temperature change in water permeability.

In practical terms, it is desirable to discuss the water permeability of the timing layer based on the time required for an alkaline processing liquid to permeate through the timing layer and its pH to decrease as alkali is absorbed into the neutralization layer.

In this case, the pH is 10 (this pH is recognized in the art as the point at which photographic development substantially stops).

), and by comparing the rate of change due to temperature with the temperature change in the transferred image density, it was found that there was a very good correlation. PH is 1
The time required for the pH to drop to zero is preferably measured using a pH indicator dye that does not decompose under alkaline conditions. Especially as a PH indicator as described later in Example 2.
It is preferable to measure by a method using thymol J-charein, which is a pigment that changes color with HlO. Using thymol phthalein and the method shown in Example 2 of the present invention, the rate of temperature change during the time when the pH of the alkaline treatment solution decreases to 10 was measured for the timing layer used in the present invention and the timing layer according to other prior art techniques. When we compared the transfer density with temperature changes, we found a clear correlation.

The measurement temperature was set at two points: 25°C, which is suitable for humans to live in, and 15°C, which is slightly lower. The preferred range of the timing layer of the present invention is preferably defined using the time required to reach PHIO at 25°C as a scale. It is preferable that the Tl5/T25 value measured according to the method of Example 2 is 250 to 600%, particularly preferably 300 to 500%. The timing layer described in the above-mentioned Japanese Patent Application Laid-Open No. 49-22935 cannot cover this range of values, and therefore, when the timing layer of this prior art is used, the temperature dependence of the transferred image density is large.

The silver halide emulsion used in the light-sensitive element in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof. hand,
The halogen composition is selected depending on the use and processing conditions of the photosensitive material, but the iodide content is 1 mol% to 10 mol% (the chloride content is 30 mol% or less), and the remainder is bromide. Silver bromide or silver chloroiodobromide agents are particularly preferred. Emulsions that easily form latent images on the grain surfaces can also be used in the present invention, but US Pat.
2, 3456953, 3761276, 3206
It is preferable to use internal latent image type direct reversal emulsions such as those described in Nos. 313, 3317322, 3761266, 3850637, 3923513, 37361401, 3761267, and 3854949.

Color image-providing materials for diffusion transfer methods used in combination with the photographic emulsion of the present invention include, for example, US Pat.
No. 227554, No. 3443939, No. 3443940, No. 3658524, No. 3698897, No. 3725062, No. 3728113, No. 3751406, 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, JP-A-49-114424, 49
-126332, 48-33826, 49-126
No. 331, No. 50-115528, No. 51-113624
Among them, it is preferable to use a diffusible dye-releasing redox compound (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-41-(2''-hydroxy-4''-
Methyl-5''-hexadecyloxyphenylsulfamoyl)-phenylazo]naphthalene, yellow dye image-forming material: 1-phenyl-3-cyano-4+-3'
+-2″-hydroxy-4″-methyl-5! 'Te2''・
Examples include 45-di-t-pentylphenoxyacetamino)-phenylsulfamoyl]phenylazo}-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, aminophenol (e.g. 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, etc. 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).

The direct reversal photographic emulsion that can be used in the present invention is developed after image exposure in the presence of a fogging agent or as disclosed in US Pat.
6953 (KnOtt,!:.Stevens), a uniform exposure (high intensity short exposure, i.e. shorter than 10-2 seconds,
However, a positive image can be directly obtained by fogging the image using low-light, long-time exposure.

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 light-sensitive material or may be added to the developer, but it is preferable to contain it in the light-sensitive material. As a fogging agent for this type of emulsion, US Pat.
Hydrazines described in No. 85, hydrazides and hydrazones described in No. 3227552, British Patent No. 128
No. 3835, Japanese Patent Publication No. 49-38164, U.S. Patent No. 37
No. 34738, No. 3719494, No. 3615615
The quaternary salt compounds described in this issue are representative.

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

The concentration of this force brushing agent is generally 50η to 10y/1 mole Agl, preferably 3
00Tf is used in the range of 9 to 5y/1 mol Ag. When adding a power brushing agent to the developer, generally developer solution 1
1 to about 0.05 to 57 (preferably 0.1 to 57)
1y).

When a power brushing agent is included in any layer of a photosensitive material, it is also effective for this purpose to make the power brushing agent diffusion resistant. An effective means for imparting diffusion resistance is to bond a ballast group, which is commonly used in couplers, to a fogging agent. 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.

In the present invention, diffusible dye releasing couplers (DDR couplers)
As a color developing agent when using
No. 27552, No. 2559643 and No. 38132
A typical example is the para-J-G nylene diamine derivative described in No. 44.

Furthermore, p-aminophenol derivatives such as those described in JP-A-48-26134 can also be advantageously used. Such color developing agents are preferably present in an alkaline developing processing composition contained in a breakable container. The color developing agent may also be contained in a separate layer in the negative portion of the film unit;
Alternatively, it can be present in the same layer as the silver halide emulsion layer. The image receiving element is made of poly-4-vinylpyridine latex (particularly
(in polyvinyl alcohol), U.S. Patent 300387
Polyvinylpyrrolidone described in No. 2, US Pat. No. 32393
No. 37, No. 3958995, No. 3770439, No. 38
No. 98088, West German patent application (0LS) 2264073
It is essential to have a mordant layer consisting of a mordant such as a polymer containing a quaternary ammonium salt or a phosphionium salt, as described in the No.

As the mordant, basic polymers described in US Pat. No. 2,882,156, ZU No. 3,625,694, US Pat.

Other mordants described in US Pat. Nos. 2,484,430, 3,271,147, 3,184,309, and 3,271,147 are also effective. The DTR color photographic elements of this invention have supports that do not undergo significant dimensional changes during processing.

Examples of such supports include cellulose acetate films and polyethylene films used in ordinary photographic materials.
Examples include tyrene film, polyethylene terephthalate film, and polycarbonate film. Other useful supports include, for example, paper and paper laminated on the surface with a water-impermeable polymer such as polyethylene. The treatment composition used in the present invention is
It is a liquid composition containing processing components necessary for developing a silver halide emulsion and forming a diffusion transfer dye image, and the main solvent is water, and in addition, a hydrophilic solvent such as methanol or methylceron lube is used. May include. 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.). Alkali include lithium hydroxide, sodium hydroxide, potassium hydroxide,
Alkali metal or alkaline earth metal salts such as calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine,
or amines are used, preferably about 1 at room temperature.
It is desirable to contain a caustic alkali having a pH of 2 or higher, particularly at a concentration of PH14 or higher. 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 at least 1 p.p., preferably several hundred (500-600) to 10.00 p.p.
It not only provides a viscosity similar to that of Pois and facilitates the uniform spread of the composition during processing, but also becomes non-fluid when the processing composition is concentrated due to the migration of aqueous solvent to the photosensitive element and image receiving element during processing. The film forms a film that helps the film units to be integrated 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 diffusely transferred dye image is substantially completed, thereby preventing changes in the image. The processing composition may also contain light-absorbing substances such as TiO2, Carbon Brass PH indicator dye, and U.S. Pat.
It may be advantageous in some cases to contain desensitizers such as those described in No.

Furthermore, a development inhibitor such as benzotriazole can be added to the processing liquid composition. The above treatment compositions are disclosed in U.S. Pat. No. 2,543,181, U.S. Pat.
It is preferable to use it in a rupturable container as described in No. 91, No. 3056492, No. 3152515, etc.

When the photographic element of the present invention is a film unit (i.e., a film unit adapted to be processed by passing the film unit between a pair of juxtaposed pressure members), it preferably
Contains the following elements: (1) to (3).

After exposure, the photosensitive element in the film unit is transferred to its image receiving element (which incorporates the neutralization system of the present invention).
and can be treated by spreading an alkaline treatment composition between the two elements.

In this case, the image receiving element may be peeled off after transfer, or the image may be viewed without being peeled off, as described in US Pat. No. 3,415,645.

In another embodiment, the image-receiving layer in the film unit can be arranged integrally with the photosensitive element together with the support. For example, Pelkey Patent No. 757960
a transparent support as disclosed in the above patent, an image-receiving layer, a substantially opaque light-reflecting layer (e.g. a TiO layer and a carbon black layer), and one or more light-sensitive silver halide emulsion layers as described above. It is effective to apply a photosensitive element composed of: After exposure of the photosensitive element, it is placed face-to-face with an opaque cover sheet (incorporating the neutralization system of the present invention) and a processing composition is spread between the two. Another embodiment of the overlapping and integrated type to which the present invention can be applied is disclosed in Pelkey Patent No. 75795.
It is disclosed in No. 9.

According to this embodiment, an image-receiving layer, a substantially opaque light-reflecting layer (such as those described above), on a transparent support,
Then, a photosensitive element consisting of one or more photosensitive layers as described above is applied, and a transparent cover sheet (incorporating the neutralization system of the present invention) is placed on the surface of the photosensitive element. A rupturable container containing an alkaline processing composition containing an opacifying agent (eg, carbon black) is placed adjacent the top layer (protective layer) of the photosensitive element and the transparent cover sheet. Such a film unit is exposed to light through a transparent cover sheet, and upon removal from the camera, the container is ruptured by a pressing member, and the processing composition (including the opacifying agent) is transferred between the photosensitive element and the cover sheet. It spreads over a whole area in between. As a result, the film unit is shielded from light and development proceeds. Other useful laminate forms in which DRR compounds or DDR couplers can be used in the present invention are U.S. Pat.
No. 7487 and No. 3635707, German Patent Application (0LS) No. 2426980.

Example 1 A neutralizing layer was coated on a polyethylene terephthalate film having a thickness of 100 μm using the recipe shown in () below, and a cellulose acetate timing layer was coated thereon using the recipe shown in (11) below.

Furthermore, a polymer latex was applied thereon as shown in Table A, and dried for 5 minutes at the drying temperature shown to form a timing layer used in the present invention. These coated products were designated as cover sheets Taki 1 to 6, respectively. Washing 5 and 6 are US Patent 4056
This invention relates to the polymer latex described in No. 394. That is, the polymer latex (a) used for waterfall 5 is acrylonitrile vinylidene monochloride-acrylic acid copolymer (weight ratio 15.0:79.0:6), and the polymer latex (b) used for waterfall 6 is is methyl methacrylate vinylidene monochloride-itaconic acid copolymer (weight ratio 15:83
:2).

(1) Coating of neutralizing layer 5+2 for 1 kg of a 20% solution of monobutyl acrylate (mole ratio 8:2) copolymer with an average molecular weight of 50,000 (solvent: acetone and water 3:1 (volume ratio)) -Dissolve cyanoethylthiodiphenyltetrazole for 3.8y.

This liquid was applied at 110y per square meter using an extrusion coater, with a wind speed of 5m/sec and a temperature of 120°C.
The film was dried for 5 minutes using dry air with a dew point of 5° C. to obtain a film with a thickness of about 20 μm. (n) Application of cellulose acetate timing layer Cellulose acetate (LM-70 manufactured by Daicel Corporation) 55 with a degree of acetylation of 52.1% (the weight of acetic acid released by hydrolysis is 0.5217 per sample 17)
7 and a styrene monomaleic anhydride (mole ratio 1:1) copolymer 5f having an average molecular weight of 10,000 are dissolved in an acetone-cyclohexanone 3:1 (volume ratio) mixed solvent.

This solution was applied onto the neutralization layer at a rate of 50% per square meter using an extrusion coater, and dried with dry air at a wind speed of 4 m/s, a temperature of 80°C, and a dew point of 5°C to obtain a film with a thickness of 2.6 μm. Ta. Example 2 The cover sheets Taki 1 to 6 produced in Example 1 were faced with a PH indicator-coated film made with the formulation shown in the following example, and in the meantime, the cover sheets 1 to 6 produced in Example 1 were coated with a PH indicator-coated film prepared by the preparation method shown in (5) below. The alkaline viscous liquid was developed to a thickness of 120 μm.

Next, the concentration is measured from the side of the PH indicator-coated film, and the time required for the reflection density of the high PH color (blue) of thymol phthalein to decrease by half due to neutralization (this time
(determined as the time to reach lO) was measured at 25°C and 15°C with and without incubation of the cover sheet. The test results are shown in Table B. 0
11 Preparation of a pH indicator-coated film A 7% gelatin solution containing 28.5η of moleputrene per 1 ton of gelatin (the solvent is water-methanol volume ratio 4:
1 mixed solvent) at a rate of 100f per square meter,
Create a film with a dry thickness of approximately 6.5μ.

A titanium dioxide dispersion (solid content concentration 10%) mixed at a ratio of 17 parts gelatin to 97 parts titanium dioxide is applied thereon at 300y per square meter to form a white film with a dry thickness of about 9μ. Further, the same thymolphthalein-containing gelatin solution as above was applied thereon in the same manner and dried to complete the process. Preparation of alkaline viscous liquid Hydroxyethyl cellulose (Nat
rOsOl25O-HR) was dissolved in 30 y of water and 30 y of sodium hydroxide was dissolved in 940 y of water with stirring, and the mixture was defoamed before use.

As is clear from the comparison of the values in Table B, when the timing layer of the present invention is used, the temperature change in water permeability is large, and even in the incubation test, the change in water permeability is small. In good condition.

On the other hand, in the comparative example, the temperature change in water permeability is large, but the water permeability easily changes due to incubation. Example 3 Cover sheet produced in Example 1 (.461-6
), the cover sheet was subjected to a forced deterioration test in order to check whether the alkali permeability of the cover sheet decreases due to being sandwiched between metal blocks during heat sealing and causes fogging or staining in the surrounding developed area. The presence or absence of fogging and staining was examined using two metal blocks (with a width of 5 m0 and sandwiched for 1 second) whose central portions were heated to 120°C.

(5) Red-sensitive internal latent image type direct reversal silver iodobromide emulsion (in silver halide... halogen composition: iodine 2 mol%, silver amount 1.97/I, gelatin 1.4% photosensitive) Preparation of Sheet On a transparent polyethylene terephthalate support with a thickness of 180μ, the following layers were provided in order: (1) The following mordant (3)
．． (2) Layer containing titanium dioxide (20y/TI) and gelatin (2.07/7rI) (3) Carbon black (2.57/TI) and gelatin (2.57/m”)
Layer (4) containing the following cyan image-providing material (0.507/
TI), diethyl laurylamide (0.25y/M2)
and a layer containing gelatin (1.14y/Trl) and sodium pentadecylhydroquinone sulfonate (0.13y/Trl).
(7/Tll) layer (6) containing gelatin (2,67/Tr
l) and 2,5-dioctylhydroquinone (1.0y/
Layer containing M2) 10(7) The following magenta color image-providing substances (0.45 Z/m"), diethyl laurylamide (0,107/I), 2,5-di-t-butylhydroquinone (0.00747 /d)), and gelatin (0
．． Layer (8) containing green-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition of silver iodobromide: 2 mol% iodine, 1.4 f/I in silver amount, gelatin) 1.07/
M2), the same fogging agent (
0.247/d) and sodium pentadecylhydroquinone sulfonate (0.117/M2) (9)
Layer containing gelatin (2.67/Tl), 2,5-dioctylhydroquinone (1.0y/wl) 0) The following yellow one-color image-giving material (0.787/wl), diethyl laurylamide (0.16f/wl) d), 2,5-di-t-butylhydroquinone (0.0127/i) and gelatin (
0.787/TI) containing a blue-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition of silver iodobromide: 2 mol% iodine, 2.2 t/I in terms of silver content). , gelatin 1.7r
/7rI), the same fogging agent added to layer (5) above (0.020ft/I) and sodium pentadecylhydroquinone sulfonate (0.094f7/Trl).
) Layer treatment solution containing gelatin (0.94 t/a) 0.87 portions of the treatment solution having the above composition were filled into containers that can be broken under pressure.

Processing process The test cover sheet described above and the photosensitive sheet were overlapped, and the color test chart was exposed from the side of the cover sheet, and then the processing solution was spread between the two sheets to a thickness of 85μ. was done with the help of a pressure roller).

The treatments were carried out at 25°C and 15°C, respectively. When cover sheets Taki (1) to (4) were used, there was no change in image density in the area heated between the metal blocks and other areas, but when cover sheets Taki (5) and (6) were used, the image density remained unchanged. When the area was heated by the metal block, the increase in image density was more noticeable than in the other areas, and the occurrence of stains was also large. Preferred embodiments of the present invention are listed below, but the present invention is not limited thereto.

(1) The photographic element claimed is a cover sheet.

(2) A photosensitive sheet comprising an image-receiving element and a photosensitive element sequentially coated on a support, a cover sheet having a neutralization system, and a photographic element according to the claims spread between the photosensitive element and the cover sheet. The processing elements are preferably integrated (however, these elements may be detachable if necessary).

) Must be a laminated integrated film unit. (3) In embodiment 2, the photosensitive element has at least one silver halide photographic emulsion layer in combination with a dye image-providing material.

(4) In Embodiment 3, the dye image-providing substance is contained in a layer adjacent to the photographic emulsion layer.

(5) In Embodiment 3, the dye image-providing substance is a compound that releases a diffusible dye when oxidized by an oxidation product of a developing agent. (6) In Embodiment 3, the photographic emulsion is a direct reversal photographic emulsion.

(7) In Embodiment 6, the direct reversal photographic emulsion is an internal latent image type direct reversal photographic emulsion.

(8) In Embodiment 7, the internal latent image emulsion is a core/shell type internal latent image emulsion.

(9) The dye image-providing material in embodiment 5 is combined directly with the reversal photographic emulsion layer.

AO) In the claimed photographic elements, no water-soluble substances other than surfactants used as emulsifiers or coating aids are included in the preparation of the latex for the timing layer and in the formation of the timing layer from the latex.

In the claimed photographic element, the neutralizing system has Tl as measured by the test method set forth in Example 2.
The value of 5/T25 (ratio of time required to lower the pH of the alkaline treatment agent to 10 at 15°C and 25°C) is in the range of 250% to 600%.

(auto) Tl5/T25 in the photographic element of embodiment 11
The value of is in the range of 300% to 500%.

Claims (1)

[Claims] 1. A neutralization system for lowering the pH of an aqueous alkaline developer [This neutralization system includes a neutralization layer and a timing layer, in which the developer passes through the timing layer. The neutralization layer is superimposed (directly or indirectly) on or below the neutralization layer in such a positional relationship that the neutralization layer is reached through the neutralization layer. ] in a photographic element for color diffusion transfer, wherein the timing layer is formed from at least one polymer latex represented by the following general formula I (
1. A photographic element for color diffusion transfer, characterized in that the polymer latex layer is water permeable. General formula I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is hydrogen or methyl group, Z is ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼, R_2 is an alkylene group with 2 to 10 carbon atoms (this (The group may be further substituted) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_3 is an alkylene group having 2 to 6 carbon atoms (this group may be further substituted), and A is copolymerizable. a, b, and c represent the copolymerization monomer ratio (% by weight). a is 50-90, b is 0.5-20, and c is 0-50. n is an integer of 1 to 5, M is hydrogen, alkali metal or ammonium radical (
NH_4). ].